NEW BRANCHED POLYMERS, THEIR PREPARATION PROCESS, AND USES THEROF

Abstract

The present invention concerns a polymer comprising:—at least one repetitive unit (V) having the following formula (T):(T)—and preferably at least one, preferably at least two, repetitive unit(s) (U) having the following formula (D):(D).

##STR00001##

Claims

1. A polymer comprising: i) at least one repetitive unit (V) having the following formula (T): ##STR00081## and ii) at least one repetitive unit(s) (U) having the following formula (D): ##STR00082## or at least one repetitive unit(s) (Q) having the following formula (S): ##STR00083## or at least one repetitive unit(s) (Q) having the following formula (S′): ##STR00084## wherein: A.sub.1 represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms; A.sub.4 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms; A.sub.2 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms; A.sub.3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms; R.sub.1, R′1, R.sub.2 and R.sub.3 are ##STR00085## or H; i is 0, 1 or 2; j is 0 or 1; i being 0 when j is 1 and j being 0 when i is 1 or 2; when A.sub.1 is H and i is 0, then A.sub.2 is a bond, and wherein: in the unit (U) having the formula (S), only one of R.sub.1, R.sub.2 and R.sub.3 is H ; in the unit (U) having the formula (S′), one or two of R.sub.1, R′.sub.1, R.sub.2 and R.sub.3 is H.

2. The polymer according to claim 1, further comprising at least one repetitive unit (W) having the following formula (L): ##STR00086## wherein: A.sub.1, A.sub.2, A.sub.3, A.sub.4, i and j are as defined in claim 1; and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being ##STR00087## or H, three of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being H.

3. The polymer according to claim 1, wherein the number-average molecular weight Mn is comprised between 3 000 g/mol and 500 000 g/mol.

4. The polymer according to claim 1, comprising at least three repetitive units (V) having the formula (T).

5. The polymer according to claim 1, wherein the repetitive unit (U) has one of the following formulae (D1), (D2) or (D3): ##STR00088## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1.

6. The polymer according to claim 1, wherein the repetitive unit (V) has the one of the following formulae (T1), (T2) or (T3): ##STR00089## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1.

7. The polymer according to claim 1, comprising: at least one repetitive unit (W) having the following formula (L1): ##STR00090## and/or at least one repetitive unit (W) having the following formula (L2): ##STR00091## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1; or at least one repetitive unit (W) having the following formula (L3): ##STR00092## and/or at least one repetitive unit (W) having the following formula (L4): ##STR00093## and/or at least one repetitive unit (W) having the following formula (L5): ##STR00094## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1; or at least one repetitive unit (W) having the following formula (L6): ##STR00095## and/or at least one repetitive unit (W) having the following formula (L7): ##STR00096## and/or at least one repetitive unit (W) having the following formula (L8): ##STR00097## and/or at least one repetitive unit (W) having the following formula (L9): ##STR00098## wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1.

8. The polymer according to claim 1, wherein: A.sub.1 represents H, i is 0, j is 0, A.sub.2 represents a bond, and A.sub.3 and A.sub.4 represent a butylene radical; or A.sub.1 represents H, i is 1, j is 0, A.sub.2 represents a pentylene radical, A.sub.3 represents a propylene radical and A.sub.4 represents a butylene radical; or A.sub.1 represents a hexyl group, i is 0, j is 0, A.sub.2 represents an ethylene radical, A.sub.3 represents a pentylene radical and A.sub.4 represents a hexylene radical; or A.sub.1 represents a pentyl group, i is 2, j is 0, A.sub.2 represents a methylene radical, A.sub.3 represents a propylene radical and A.sub.4 represents a butylene radical; or A.sub.1 represents a heptyl group, i is 0, j is 0, A.sub.2 represents a methylene radical, A.sub.3 represents a methylene radical and A.sub.4 represents a hexylene radical; or A.sub.1 represents a hexyl group, i is 1, j is 0, A.sub.2 represents a methylene radical, A.sub.3 represents a methylene radical and A.sub.4 represents a hexylene radical.

9. A process for preparing a polymer according to claim 1, comprising a step of polymerization of at least one monomer of formula (IV): ##STR00099## wherein: A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are as defined in claim 1; Y represents —OR.sub.a, R.sub.a being a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms; said step being carried out in the presence of a catalyst selected from the group consisting of: NaOMe, Zn(OAc).sub.2, Ti(OBu).sub.4, Ti(OiPr).sub.4, Sb.sub.2O.sub.3, stannous octanoate, dibutyltin oxide, 7-methyl-1,5,7-triazabicyclo(4.4.0)dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene, said process optionally comprising a step of recovering said polymer.

10. The process of claim 9, wherein the catalyst is Zn(OAc).sub.2, NaOMe or 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

11. The process according to claim 9, wherein the amount of catalyst is comprised from 0.05% to 10% by weight relative to the weight of the monomer of formula (IV).

12. The process according to claim 9, wherein the polymerization step is carried out by heating the monomer of formula (IV) as defined in claim 9 in the presence of the catalyst, at a temperature T1 comprised from 90° C. to 130° C. for 1 hour to 48 hours, then by heating further at a temperature T2 comprised from 90° C. to 180° C. for 1 hour to 48 hours.

13. A polymer susceptible to be obtained according to the process according to claim 9.

Description

EXAMPLES

Suppliers

[0343] 1,5,7-triazabicyclo[4.4.0]dec-5-ene (98%), zinc acetate (99.99%), dibutyltin oxide (98%), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, tin (II) 2-ethylhexanoate (95%) were obtained from Sigma Aldrich. Titanium (IV) n-butoxide (99%) and titanium (IV) isopropoxide (98+%) were purchased from Acros Organics. Antimony (III) oxide (99.6% min.) was supplied by Alfa Aesar. All products were used as received.

Analyses

[0344] The conditions of the steric exclusion chromatography were as follows: [0345] Columns TSKgel TOSOH [0346] HXL-L (guard 6*40) [0347] G4000HXL (7.8*300) [0348] G3000HXL (7.8*300) [0349] G2000HXL (7.8*300) [0350] Flow 1 mL/min [0351] Flow marker TCB for trichlorobenzene (1 mL/500 mL THF) [0352] Four 40° C. [0353] Loop 20 μL [0354] Calibration Polystyrene standards from polymer laboratories

A. Monomers

[0355] The following monomers have been used:

##STR00080##

[0356] The monomer (1) has been prepared following a two-step procedure. Methyl esters of high oleic sunflower oil and formic acid (0,3 n) were added in a 100 L reactor equipped with a mechanical stirrer and a condenser, n being the number of mole of double bond on the methyl esters. The resulting mixture was heated at 70° C. for 1 hour under stirring. At 70° C., hydrogen peroxide (35%, 2 n) was added slowly to the reactor using a volumetric pump while maintaining the temperature in the reactor close to 75-80° C. When the addition was finished, the temperature was risen to 90° C. for 2 hours. The reaction was monitored by gas chromatography. The reaction mixture was then cooled down to 40° C. temperature and the aqueous phase was discarded. The organic layer was washed with an aqueous solution of sodium hydroxide (0.1 N) until the pH becomes neutral. The organic phase was finally dried under vacuum to afford a clear and slightly yellow liquid (Oxiran number ˜5.0%). In a second step, 1 portion of epoxydized methyl esters of oleic sunflower oil was placed along with ½ portion of an aqueous solution of phosphoric acid (12% w/w) and ⅓ portion of tert-butanol as solvent in a 100 L reactor equipped with a condenser and a mechanical stirrer. The resulting mixture was then heated at 90° C. under vigorous stirring. The reaction was monitored by gas chromatography. When the reaction was completed the aqueous phase was discarded at 50° C. The tert-butanol was eliminated under vacuum distillation. The organic phase was then washed with hot water until the pH reaches 6-7 and dried under vacuum. The methyl 9,10-dihydroxystearate (1) was recrystallized in cyclohexane to afford a white solid powder. The yield of the two-step synthesis of methyl 9, 10-dihydroxystearate is about 90%.

[0357] The monomer (2) has been prepared following a two-step procedure. Methyl esters of castor oil and formic acid (0,3 n) were added in a reactor equipped with a mechanical stirrer, a dropping funnel and a condenser, n being the number of mole of double bond of the methyl esters. The resulting mixture was heated at 40° C. for 1 hour under stirring condition. At 40° C., hydrogen peroxide (50%, 2 n) was added drop wise to the reactor using a dropping funnel while maintaining the temperature in the reactor close to 70 75° C. The reaction was monitored by gas chromatography. The reaction mixture was then cooled down to room temperature and the aqueous phase discarded. The organic layer was washed with an aqueous solution of sodium hydroxide (0.1N) until the pH becomes neutral. The organic phase was then dried under vacuum at 60° C. to afford a clear and slightly yellow liquid with a precipitate. The precipitate isolated by filtration is the methyl 9, 10, 12-trihydroxystearate, the yellow liquid corresponds to the epoxidized methyl esters of castor oil.

[0358] In a second step, 1 portions of epoxidized methyl esters of castor oil was placed along with ½ portion of an aqueous solution of phosphoric acid (12% w/w) and 1/3 portion of tert-butanol as solvent in a reactor equipped with a condenser and a mechanical stirrer. The resulting mixture was then heated at 90° C. under vigorous stirring. The reaction was monitored by gas chromatography. When the reaction was completed the aqueous phase was discarded at 50° C. The tert-butanol was eliminated under vacuum distillation. The organic phase was then washed with hot water until the pH reaches 6-7 and dried under vacuum. The methyl 9, 10, 12-trihydroxystearate (2) was then recrystallized in cyclohexane to afford a white solid powder in a 25% yield.

[0359] The monomer (3) has been previously prepared by the process as described in U.S. Pat. No. 5,344,946.

[0360] The monomer (4) has been prepared by esterification of aleuritic acid in methanol. A round-botttomed flask was charged with 5 g of aleuritic acid, 50 mL of methanol and 1 g of Amberlyst 15. The mixture was heated at 70° C. under reflux for 24 hours. After reaching rt, the resin was filtered, the methanol removed under vacuum and 100 ml of DCM was added. The organic phase was washed twice with water, dried on anhydrous magnesium suflate and DCM was removed under vacuum. Monomer (4) was thus obtained as a white solid powder (yield: 75%).

[0361] Refined erucic acid rapeseed oil (800 Kg) was heated under stirring condition at 65° C. in the presence of methanol (190 Kg) and sodium methanolate (19 Kg) for 2 hours. The thus-obtained methyl esters were decanted and the glycerol phase discarded. Methyl esters of erucic acid rapeseed oil were then washed with water, dried under vacuum and distilled on a falling film reactor (200 L/hour) in order to concentrate the erucic acid methyl ester up to 95%. The procedure followed to prepare the monomer (5) starting from methyl erucate was identical to the one described earlier to obtain the monomer (1).

B. Preparation of the Branched Polymers

General Procedure

[0362] 0.500 g of a monomer was added to a Schlenk flask equipped with a magnetic stirrer, a nitrogen inlet tube and an oil-bath heating system. The monomer was firstly is dried alone under dynamic vacuum, above its melting point at 90° C. This pre-drying step took one hour, then the reaction mixture was placed under nitrogen blowing, the temperature was raised to 120° C. and 7.5 mg (1.5 wt %) of catalyst was introduced in the reaction flask. The mixture was subsequently allowed to react under stirring at 120° C. during 2 hours. Finally, the temperature was raised to 160° C. or 170° C. and dynamic vacuum was applied for 13 hours in order to remove the released methanol. The crude product was obtained as a colorless and highly viscous material. It was purified by precipitation from THF to pentane.

[0363] Six branched polymers were prepared according to the general procedure mentioned above. Such polymers derived from the above-mentioned monomers (1), (2), (3), (4), (5) and (6).

Example 1

Polyester Derived From Monomer (1)

[0364] Different polyesters were synthesized according to the general procedure as described above.

TABLE-US-00001 T Conversion M.sub.n M.sub.w Entry Catalyst.sup.a (° C.).sup.b (%).sup.c (g .Math. mol.sup.−1).sup.c (g .Math. mol.sup.−1).sup.c  .sup.c DB.sup.d 1 Ti(OBu).sub.4 170 64 1300 1490 1.15 0 2 Zn(OAc).sub.2 170 98 6280 96500  >15.4 0.08 3 DBTO 170 67 1270 1430 1.13 0.06 4 Sb.sub.2O.sub.3 170 71 1450 1750 1.21 0.08 5 TBD 170 100 4220 14070  3.33 0.23 6 Zn(OAc).sub.2 160 98 3480 9530 2.74 0.02 7 TBD 160 100 4080 10110  2.48 0.21 8 NaOMe 160 100 6 100  18 800   3.08 0.29 .sup.aLoading in catalyst: 1.5 wt %. .sup.bTemperature of the last stage of polymerization. .sup.cSEC in THF, PS calibration. .sup.d1H-NMR.   : dispersity, DB: degree of branching

[0365] The conversion corresponds to the percentage by weight of conversion of the monomer (1).

[0366] M.sub.n, M.sub.w and were determined by steric exclusion chromatography in THF with polystyrene standards, and the degree of branching was determined by RMN .sup.1H.

[0367] Thermo-mechanical properties of the renewable polymers obtained were characterized by Differential Scanning calorimetry (DSC) and Thermal Gravimetric Analysis (TGA).

[0368] Highly branched polyesters displayed amorphous properties with glass transition temperature in the range −32.5° C. to −20° C. for polyesters derived from the polymerization of monomer (1). Some results are provided in the following table:

TABLE-US-00002 Loading in catalyst Conversion M.sub.n T.sub.g.sup.c T.sub.10%.sup.d Catalyst (wt %) (%).sup.a (g .Math. mol.sup.−1).sup.a  .sup.a DB.sup.b (° C.) (° C.) Stannous 1.5 93 3160 2.04 0.11 −30 284 octoate Zn(OAc).sub.2 1.5 98 3480 2.74 0.02 −27 266 TBD 1.5 100 5340 2.97 0.21 −24 339 TBD 5 100 9825 3.37 0.28 −20 340 .sup.aSEC in THF, PS calibration. .sup.b1H-NMR. .sup.cDSC. .sup.dTGA.   : dispersity, DB: degree of branching
The resulting polymers provide the following RMN.sup.1H spectrum:

.SUP.1.H NMR (400 MHz, DMSO) δ 4.91, 4.71, 4.70, 4.69, 4.60, 4.59, 4.09, 3.57, 3.39, 3.18, 2.50, 2.27, 2.27, 2.25, 2.24, 1.52, 1.37, 1.23, 1.02, 0.87, 0.85, 0.83, 0.62.

Example 2

Polyester Derived From the Monomer (2)

[0369] Different polyesters were synthesized according to the general procedure as described above.

TABLE-US-00003 T Conversion.sup.a M.sub.n.sup.a T.sub.g.sup.b T.sub.10%.sup.c Catalyst.sup.a (° C.).sup.b (%) (g .Math. mol.sup.−1)  .sup.a (° C.) (° C.) Zn(OAc).sub.2 160 97 3800 2.57 −2.5 271 TBD 160 100 5540 4.09 −0.9 323 NaOMe 160 98 4600 2.83 3.3 320 .sup.aSEC in THF, PS calibration .sup.bDSC. .sup.cTGA.   : dispersity
The conversion corresponds to the conversion of the monomer (2).
Highly branched polyesters displayed amorphous properties with glass transition temperature in the range from −13.2 to 0.6° C. for polyesters derived from monomer (2). M.sub.n, M.sub.w and were determined by steric exclusion chromatography in THF with polystyrene standards, and the degree of branching was determined by RMN .sup.1H.
The resulting polymers provide the following RMN.sup.1H spectrum:

.SUP.1.H NMR (400 MHz, DMSO) δ 5.17, 4.98, 4.97, 4.87, 4.77, 4.65, 4.64, 4.53, 4.32, 4.26, 4.20, 4.13, 4.10, 3.70, 3.59, 3.57, 3.49, 3.41, 3.31, 3.25, 3.17, 2.50, 2.22, 1.49, 1.39, 1.32, 1.30, 1.23, 0.85.

Example 3

Polyester Derived From Monomer (3)

[0370] Polyesters were synthesized according to the general procedure as described above.

TABLE-US-00004 Conv. M.sub.n M.sub.w Catalyst.sup.a (%).sup.b (g .Math. mol.sup.−1).sup.c (g .Math. mol.sup.−1).sup.c  .sup.b Zn(OAc).sub.2 98 2349 5622 2.39 TBD 95 2370 6390 2.70 .sup.aLoading in catalyst: 1.5 wt %. .sup.bSEC in THF.   : dispersity

[0371] As mentioned above, the monomer was firstly dried for one hour alone under dynamic vacuum, above its melting point at 90° C. The first step of polymerization was carried out at 120° C. for 2 hours and the second step of polymerization was carried out at 140° C. for 13 hours.

[0372] It can be seen from the above table that the conversions are close to 100%.

Example 4

Polyester Derived From Monomer (4)

[0373] A polyester was synthesized according to the general procedure as described above.

TABLE-US-00005 Conv. M.sub.n M.sub.w Catalyst.sup.a (%).sup.b (g .Math. mol.sup.−1).sup.c (g .Math. mol.sup.−1).sup.c  .sup.b TBD 96 3550 8510 2.40 .sup.aLoading in catalyst: 1.5 wt %. .sup.bSEC in THF.   : dispersity

[0374] As mentioned above, the first step of polymerization was carried out at 120° C. and the second step of polymerization was carried out at 140° C.

[0375] The above table corresponds to the polymerization results after two hours.

[0376] Another polymerization was also carried out as follows: pre-drying at 90° C. under dynamic vacuum, then the first step of polymerization was carried out at 90° C. under nitrogen, and the second step of polymerization was carried out at 90° C. for x hours under dynamic vacuum.

[0377] The resulting polymer was obtained:

TABLE-US-00006 x Conv. M.sub.n M.sub.w T.sub.g.sup.c T.sub.10%.sup.d Catalyst.sup.a (hours) (%).sup.b (g .Math. mol.sup.−1).sup.c (g .Math. mol.sup.−1).sup.c  .sup.b (° C.) (° C.) TBD   1 h 30 99 9270 44630 4.81 −16 358 TBD 1 h 100 9300 44 700  4.81 −15.2 358 TBD.sup.e 4 h 100 13000 75400 5.80 −14.4 342 NaOMe 2 98 4800 13900 2.9 −16.7 350 .sup.aLoading in catalyst: 1.5 wt %. .sup.bSEC in THF. .sup.cDSC. .sup.dTGA. .sup.eloading in TBD : 1 w %

Example 4

Polyester Derived From Monomer (5)

[0378] A polyester was synthesized according to the general procedure as described above.

TABLE-US-00007 Conv. M.sub.n M.sub.w T.sub.10%.sup.d Catalyst.sup.a (%).sup.b (g .Math. mol.sup.−1).sup.c (g .Math. mol.sup.−1).sup.c  .sup.b DB.sup.c (° C.) Zn(Ac).sub.2 95 3000 5800 1.93 0.09 / TBD 100 5600 17100 3.05 0.33 320 NaoMe 100 9200 30100 3.27 0.30 350 .sup.aLoading in catalyst: 1.5 wt %. .sup.bSEC in THF. .sup.c1H-NMR. .sup.dTGA.   : dispersity, DB: degree of branching

[0379] As mentioned above, the first step of polymerization was carried out at 120° C. and the second step of polymerization was carried out at 160° C.