Polypropylene backbone, and nanoporous polypropylene membrane

Abstract

The invention relates to a film Film comprising a random graft copolymer having a polypropylene (PP) backbone and from 3 to 8 polyester segments covalently bonded to said backbone, wherein the number average molecular weight (Mn) of the polypropylene backbone ranges between 10.000 and 100.000 Dalton (as determined with HT-SEC in o-DCB at 150 C.), wherein the Mn of each polyester segment ranges between 5.000 and 25.000 Daltons, wherein the amount of PP ranges between 45 and 80 mol %, wherein the amount of polyester segments ranges between 55 and 20 mol %, wherein the film has a thickness in the range of 0.01-10 mm, wherein the polypropylene and polyester domains form independently continuous phases, and wherein the mol % is calculated relative to the total moles of monomer units present in the copolymer. The invention further relates to a nano porous PP membrane and its use.

Claims

1. A film comprising a random graft copolymer having a polypropylene (PP) backbone and from 3 to 8 polyester segments covalently bonded to said PP backbone, wherein the number average molecular weight, Mn, of the PP backbone ranges between 10 and 100 kDa, wherein the M.sub.n of each polyester segment ranges between 5 and 25 kDa, wherein the amount of PP ranges between 45 and 80 mol %, wherein the amount of polyester segments ranges between 55 and 20 mol %, wherein the film has a thickness in the range of 0.01-10 mm, wherein the PP and polyester domains form gyroid bicontinuous morphology, wherein the mol % is calculated relative to the total moles of monomer units present in the copolymer wherein the polyester segments are self-arranged in domains suitable to form porous channel through the film after a segment sacrifice process.

2. The film according to claim 1, wherein the PP backbone is prepared from a PP-homopolymer or from a copolymer of propylene and ethylene, wherein the amount of ethylene is less than 5 wt %.

3. The film according to claim 1, wherein the PP in the backbone of the copolymer has a melting temperature of at least 120 C.

4. The film according to claim 1, wherein the film has a Young's modulus between 300 and 1500 MPa and the toughness of the film ranges between 1 and 150 J/m.sup.3.

5. The film according to claim 1, wherein the polyester segment comprises monomer units derived from caprolactone and/or valerolactone.

6. The film according to claim 1, wherein the amount of PP ranges between 50-75 mol %, while the amount of polyester is between 50-25 mol %.

7. A nanoporous membrane, comprising at least 90 wt % of PP, wherein the PP comprises OX functional groups randomly distributed on the polymer chain, wherein the amount of functional groups ranges between 3 and 8 per polymer chain, as determined with .sup.1H NMR and wherein X is chosen from Mg, Zn, Al, H, Li, Na or K.

8. The membrane according to claim 7, wherein the PP in the membrane has an M.sub.n between 10 and 100 kDa, and is isotactic or syndiotactic.

9. The membrane according to claim 7, wherein the membrane has a thickness between 0.01 and 10 mm, wherein the membrane has pores having a size between 10-50 nm as measured with N.sub.2-desorption according to Barret-Joyner-Halenda model and a BET surface area between 50-200 m.sup.2/g determined by the Brunauer-Emmet-Teller method.

10. The membrane according to claim 7, wherein the membrane has a melt temperature, T.sub.m between 120 C. and 160 C. as measured with DSC.

11. The membrane according to claim 7, wherein the membrane has a Young's modulus between 50 and 400 MPa and the membrane has a toughness between 0.1 and 15 J/m.sup.3.

12. An article comprising the film according to claim 1, wherein the film is a water filter or battery separator.

13. A water filter system comprising the nanoporous membrane as defined in claim 7.

14. A battery comprising the nanoporous membrane as defined in claim 7.

15. A PP membrane unit, which is a multilayer membrane or multi membranes, in which the layers or the membranes are the nanoporous membrane according to claim 7, a microporous PP membrane and/or a PP non-woven material.

16. The nanoporous membrane of claim 7, wherein the polymer chain is a homopolymer of propylene, or a copolymer of ethylene and propylene, wherein the amount of ethylene is less than 5 wt %.

Description

FIGURES

(1) FIG. 1: .sup.1H NMR spectrum of the isotactic-poly(propylene-co-undecenol) precursor used for the synthesis of iPP-g-PVL and iPP-g-PVL copolymers with the methylene proton signal connected to the pending OH groups magnified for clarity, measured in tetrachloroethane-d.sub.2 at 90 C.

(2) FIG. 2: .sup.1H NMR spectrum of the iPP-g-PVL copolymer (iPP.sub.53 mol %-g-PVL.sub.47 mol %) with the methylene proton signal connected to the pending OH groups magnified for clarity, measured in tetrachloroethane-d.sub.2 at 90 C.

(3) FIG. 3: .sup.1H NMR spectrum of the iPP-g-PCL copolymer (iPP.sub.53 mol %-g-PCL.sub.47 mol %) with the methylene proton signal connected to the pending OH groups magnified for clarity, measured in tetrachloroethane-d.sub.2 at 90 C.

(4) FIG. 4: .sup.1H NMR spectrum of the iPP-g-PVL after degradation of the PVL chains, measured in tetrachloroethane-d.sub.2 at 90 C.

(5) FIG. 5: SEC traces of isotactic-poly(propylene-co-undecenol) precursor and iPP-g-PVL copolymer (iPP.sub.53 mol %-g-PVL.sub.47 mol %).

(6) FIG. 6: AFM of the cross-section of iPP-g-PVL copolymer (iPP.sub.53 mol %-g-PVL.sub.47 mol %) a) and b) before degradation c) and d) after degradation.

(7) FIG. 7: Stress-strain curves of the tensile testing of a) iPP-g-PVL copolymer (iPP.sub.53 mol %-g-PVL.sub.47 mol %) before (solid line) and after degradation of PVL (dash line) and b) iPP-g-PCL copolymer (iPP.sub.53 mol %-g-PCL.sub.47 mol %) before (solid line) and after degradation of PCL (dash line).

(8) FIG. 8: FE-SEM of the porous membranes from a) iPP-g-PVL copolymer (iPP.sub.53 mol %-g-PVL.sub.47 mol %) after degradation; b) iPP-g-PCL copolymer (iPP.sub.53 mol %-g-PCL.sub.47 mol %) after degradation.

(9) FIG. 9: a) Nitrogen adsorption measurements on porous membranes measured at T=77K showing the adsorption (filled squares) and desorption (empty squares) isotherms; b) Pore size distribution for the porous membranes after PVL or PCL degradation calculated from nitrogen adsorption (filled squares) and desorption (empty squares) isotherms.

(10) FIG. 10: Filtration setup.

(11) FIG. 11: DLS of the silica nanoparticles dispersion before and after filtration.

(12) FIGS. 12: 3D simulation representation of embodiments: 12a, 12e and 12f are comparative examples, which are not within the scoop of the invention; 12b, 12c and 12d are embodiments within the scoop of the invention.

REFERENCES

(13) [1] (a) Baker, R. W. Membrane Technology and Applications, Wiley, West Sussex, 2004. (b) Nunes, S. P.; Car, A. Ind. Eng. Chem. 2013, 52, 993-1003. [2] (a) Bierenbaum, H. S.; Isaacson, R. B.; Druin, M. L.; Plovan, S. G. Ind. Eng. Chem. Proc. Res. Dev. 1974, 13, 2-8. (b) Chen, R. T.; Saw, C. K.; Jamieson, M. G.; Aversa, T. R.; Callahan, R. W. J. Appl. Polym. Sci. 1994, 53, 471-483. [3] (a) Fleisher, R. L.; Alter, H. W.; Furman, S. C.; Price, P. B.; Walker, R. M. Science 1972, 172, 225-263. (b) Awasthi, K.; Kulshrestha, V.; Acharya, N. K.; Singh, M.; Vijay, Y. K. Eur. Polym. J. 2006, 42, 883-887. [4] (a) Ichikawa, T.; Takahara, K.; Shimoda, K.; Seita, Y.; Emi, M. U.S. Pat. No. 4,708,800; Terumo Kabushiki Kaisha, 1987. (b) Chau, C. C.; Im, J.-h. U.S. Pat. No. 4,874,568; The DOW Chemical Company, 1989. (c) Lopatin, G.; Yen, L. Y.; Rogers, R. R. U.S. Pat. No. 4,874,567; Milipore Corporation, 1989. [5] For example see: (a) Zhang, Y.; Sargent, J. L.; Boudouris, B. W.; Phillip, W. A. J. Appl. Polym. Sci. 2015, DOI: 10.1002/APP.41683. (b) Nunes, S. P. Macromolecules 2016, 49, 2905-2916. [6] (a) Smith, D. R.; Meier, D. J. Polymer 1992, 33, 3777-3782. (b) Ndoni, S.; Vigild, M. E.; Berg, R. H. J. Am. Chem. Soc. 2003, 125, 13366-13367. (c) Zalusky, A. S.; Olayo-Valles, R.; Wolf, J. H.; Hillmyer, M. A. J. Am. Chem. Soc. 2002, 124, 12761-12773. [7] (a) Ring, J. O.; Thomann, R.; Mllhaupt, R.; Raquez, J.-M.; Dege, P.; Dubois, P. Macromol. Chem. Phys. 2007, 208, 896-302. (b) Pitet, L. M.; Amendt, M. A.; Hillmyer, M. A. J. Am. Chem. Soc. 2010, 132, 8230-8231. (c) Hillmyer, M.; Pitet, L.; Amendt, M. (University of Minnesota) U.S. Pat. No. 9,051,421 B2, 2015. (d) Kato, T.; Hillmyer, M. A. ACS Appl. Mater. Interfaces 2013, 5, 291-300. (e) Pillai, S. K. T.; Kretschmer, W. P.; Trebbin, M.; Fsrster, S.; Kempe, R. Chem. Eur. J. 2012, 18, 13974-13978. [8] The only example reported so far consist of nonporous poly(vinylidene fluoride)-graft-poly(meth)acrylate graft copolymers. For example see: Hester, J. F.; Banerjee, P.; Won, Y.-Y.; Akthakul, A.; Acar, M. H.; Mayes, A. M. Macromolecules 2002, 35, 7652-7661. [9] Wolf, J. H.; Hillmyer, M. A. Langmuir 2003, 19, 6553-6560. [10] Brunauer, S.; Deming, L. S.; Deming, W. E.; Teller, E. J. J. Am. Chem. Soc. 1940, 62, 1723-1732. [11] Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373-380.

(14) Experimental Section.

(15) Measurement Methods

(16) Materials. -Valerolactone (VL; 98%, TCI) -caprolactone (CL; 97%, Sigma-Aldrich) were dried over CaH.sub.2 (95%, Sigma-Aldrich) and distilled under reduced pressure. Diethyl ether was used as received. Toluene (anhydrous, Sigma-Aldrich) was purified using an MBraun-SPS-800 purification column system and were kept in glass bottle with 4- molecular sieves under an inert atmosphere. 10-undecen-1-ol was purchased from Sigma-Aldrich and dried with 4-A molecular sieves under an inert atmosphere. Methylaluminoxane (MAO) (30 wt. % solution in toluene) was purchased from Chemtura. Diethyl zinc (DEZ) (1.0 M solution in hexanes), triisobutylaluminium (TiBA) (1.0 M solution in hexanes). rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 was purchased from MCAT GmbH, Konstanz, Germany. Isotactic polypropylene (i-PP) (SABICPP520P, MFR=10.5 g/10 min (230 C./2.16 kg), tin(II) 2-ethylhexanoate (Sn(Oct).sub.2) (92-100%, Sigma-Aldrich), titanium (IV) n-butoxide (Ti(OBu).sub.4, Sigma Aldrich), Irganox 1010 (antioxidant, BASF) were used as received.

(17) Synthesis of isotactic poly(propylene-co-10-undecen-1-ol) (i PP-OH). The copolymerisation reaction was carried out in a stainless steel Buchi reactor (300 mL). Prior to the polymerisation, the reactor was dried in vacuo and flushed with nitrogen. Toluene (100 mL) was introduced into the reactor followed by TiBA (1.0 M solution in hexanes, 5 mL) and the functionalised comonomer (10-undecen-1-ol; 1 mL, 2.5 mmol) under a nitrogen atmosphere. The resulting solution was stirred for 15-20 min. Subsequently MAO (30 wt. % solution in toluene, 2.0 mL) was introduced into the reactor under nitrogen atmosphere. The solution was saturated with propylene (5 bar). In a glovebox, a stock solution of rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2 (5 mg, 8 mol) in toluene (10 mL) was prepared and the catalyst solution (5 mL) was transferred into the reactor under an nitrogen atmosphere. The propylene pressure was maintained constant for 30 min. At the end of the reaction, the propylene feed was stopped and the residual propylene was released from the reactor. The resulting mixture was quenched in acidified methanol (300 mL, 2.5 wt. % of concentrated HCl), filtered and washed with demineralised water. The obtained powder was dried in a vacuum oven under reduced pressure at 60 C. overnight.

(18) Typical polymerisation procedure of PP-craft-PCL via catalytic ring-opening polymerisation. iPP-OH (4 g, M.sub.n=27.8 kDa, .sub.M=2.3) was placed in a round bottom flask with a magnetic stirrer and dried by Dean-Stark distillation in toluene (100 mL) for 24 h. Than the solution was cooled down to 100 C. and catalyst Sn(Oct).sub.2 (180 mg), -caprolactone (10.3 g, 89.9 mmol) were added. The reaction was carried out for 24 h under inert atmosphere. The progress of the copolymerisation was followed by .sup.1H NMR spectroscopy by taking aliquots at set time intervals. The synthesised copolymer was isolated by the precipitation in diethyl ether and dried in a vacuum oven at 40 C. for 24 h.

(19) Typical polymerisation procedure of PP-graft-PVL via catalytic ring-opening polymerisation. iPP-OH (4 g, M.sub.n=27.8 kDa, .sub.M=2.3) was placed in a round bottom flask with a magnetic stirrer and dried by Dean-Stark distillation in toluene (100 mL) for 24 h. Than the solution was cooled down to 100 C. and catalyst Sn(Oct).sub.2 (180 mg), -valerolactone (10.0 g, 100 mmol) were added. The reaction was carried out for 24 h under inert atmosphere. The progress of the copolymerisation was followed by .sup.1H NMR spectroscopy by taking aliquots at set time intervals. The synthesized copolymer was isolated by the precipitation in diethyl ether and dried in a vacuum oven at 40 C. for 24 h.

(20) Typical procedure for the synthesis of PP-graft-PCL copolymers via transesterification reaction. iPP-OH (4 g, M.sub.n=27.8 kDa, DM=2.3) and PCL (6 g, M.sub.n=42.0 kDa, DM=2.7) with antioxidant Irganox 1010 (2500 ppm) were premixed for 5 minutes and fed into a co-rotating twin-screw mini-extruder at 190 C. with a screw rotation rate set at 100 rpm. After this time tin (II) 2-ethylhexanoate (0.09 g, 0.22 mmol) as catalyst was added and the mixture was stirred for an additional 5 minutes. Afterwards the extruder chamber was cooled and evacuated.

(21) Compression-molding experiments. All the films were prepared via compression-molding using PP ISO settings on LabEcon 600 high-temperature press (Fontijne Presses, the Netherlands). The copolymers were introduced into a Teflon mould to prepare the samples with the thickness of 0.18 mm. The program of compression molding consisted of following steps: heating to 200 C. for 5 min at 5 bar and cooling to room temperature for 10 min at 5 bar.

(22) Membrane Formation:

(23) The degradation of the polyester sequence of the copolymers was carried out by immersing pieces of the copolymer films in a 0.5 M solution of NaOH in a mix a water and methanol (60:40). The solution was kept at 70 C. during 3 days and the porous membranes were then washed with slightly acidic MeOH (aq) and then pure MeOH and dried for 24 h under vacuum.

(24) Filtration Procedure:

(25) The volumetric flux of the membrane was determined by the following procedure. The porous membrane was clamped on a glass filter device, then vacuum was applied (20 mbar) and water was added at the top of the filtration device.

(26) The volumetric flux was calculated using the Equation 1 and was equal to 75 L.Math.m.sup.2.Math.h.sup.1.

(27) $\begin{array}{cc}{J}_V=\frac{V}{A*t}& \mathrm{Equation}1:\mathrm{Volumetric}\mathrm{flux}\end{array}$

(28) Where J.sub.V is the volumetric flux, V is the volume (L), A is the area of the membrane (m.sup.2) and t is the time (h).

(29) Then, a filtration experiment was carried out using a dispersion of silica nanoparticles 3% (w/v) in ethanol (size of the particles lower than 100 nm). The dispersion was filtered using the same filtration setup and DLS experiments were carried out on the solutions before and after filtration. After filtration, no signal were measured by DLS, proving that the silica nanoparticles were stopped by the porous membrane.

(30) Characterisation.

(31) .sup.1H NMR: carried out at 90 C. using deuterated tetrachloroethane (TCE-d.sub.2) as the solvent and recorded in 5 mm tubes on a Bruker spectrometer operating at frequencies of 300 MHz. Chemical shifts in ppm versus TCE-d.sub.2 were determined by reference to the residual solvent signal.

(32) HT-SEC: M.sub.n, M.sub.w and the polydispersity index (PDI, .sub.M) were determined by size exclusion chromatography: SEC measurements were performed at 150 C. on a Polymer Char GPC-IR built around an Agilent GC oven model 7890, equipped with an autosampler and the Integrated Detector IR4. 1,2-dichlorobenzene (o-DCB) was used as an eluent at a flow rate of 1 mL/min. The SEC-data were processed using Calculations Software GPC One.

(33) DSC: Melting (T.sub.m) and crystallisation (T.sub.c) temperatures as well as enthalpies of the transitions were measured by differential scanning calorimetry (DSC) using a DSC Q100 from TA Instruments. The measurements were carried out at a heating and cooling rate of 10 C..Math.min.sup.1 from 60 C. to 230 C. The transitions were deduced from the second heating and cooling curves.

(34) Field Emission Scanning Electron Microscopy (FE-SEM) imaging. The cross-section morphology of the degraded self-assembled copolymer film was characterised by FE-SEM imaging (JEOL JSM 7800-F) at an operation voltage of 5 kV using LED detector. To obtain an adequate contrast of the membrane nano-pore morphology and to avoid destroying of the cross-sections of the membrane film, the samples for FE-SEM imaging were first immersed in liquid nitrogen, fractured and then sputtered with Platinum/palladium (Pt/Pd).

(35) Atomic Force Microscopy (AFM) Analysis.

(36) Sample preparation: For spin-coated self-assembled copolymer film, AFM imaging was directly performed on the film surface at ambient conditions without further treatment of the sample. For imaging the cross-section of the film before and after degradation, the samples were cut into proper specimens and subsequently cryo-microtomed at 120 C. using microtoming equipment (LEICA EM UC7). A diamond knife (Diatome) mounted in a stainless steel holder was used for microtoming of the samples. Such cross-sectioned segments were used for AFM measurements without further treatment.

(37) AFM analysis: AFM imaging was performed at Dimension FastScan AFM system from Bruker utilising tapping mode AFM tips (Model TESPA-V2, k: 42 N/m, f: 320 kHz). The software Nanoscope Analysis 1.5 from Bruker was used as the computer interface for operation and analysis of AFM measurements. All AFM measurements were performed at ambient conditions. Height and phase images were recorded simultaneously at a scan rate of 1 Hz with a resolution of 512512 pixels. Optical imaging integrated in the AFM setup was first used before AFM measurement to select the area of interest for imaging. Pore-size analysis: The nitrogen adsorption-desorption isotherms were measured at 196 C. using a Micromeritics ASAP 2420 analyser. The samples were degassed overnight at 30 C. under high vacuum (133 Pa) prior to measurements. The specific surface area of the membranes was calculated using the Brunauer-Emmet-Teller method,[10] while the pore-size distribution was determined using the Barret-Joyner-Halenda model.[11]

(38) Dynamic mechanical thermal analysis: DMTA was performed using a TA Instruments Q800 DMA. Samples were tested by strain controlled temperature ramp with the frequency of 1 Hz. The temperature profile was from 100 C. until the melting point of the polyolefin segment with the ramp 3 C./min. The glass transition temperature was calculated as the peak of the tangent delta signal.

(39) Mechanical properties analysis: Mechanical properties were characterised by performing tensile test experiments in triplicate, using a microtensile tester (Linkam, TST 350). Both ends of the tensile specimen (length: 30 mm, width: 2 mm, thickness: 0.18 mm) were gripped by jaws which were 15 mm apart. A load cell with a capacity of 200 N was used to measure the applied force. The tensile tests were carried out at a constant speed of 50 pm/s at room temperature.

(40) TABLE-US-00001 TABLE 1 Composition (volume and molar fraction) of the copolymers (determined by .sup.1H NMR). Propylene lactone f(PP) f(Polyester) unit unit (volume (volume #OH/ (mol %) (mol %).sup.a fraction) fraction) chain iPP.sub.52 mol %-g- 52 48 0.35 0.65 3 PVL.sub.48 mol % iPP.sub.53 mol %-g- 53 47 0.36 0.64 6 PVL.sub.47 mol % iPP.sub.56 mol %-g- 56 44 0.39 0.61 6 PVL.sub.44 mol % iPP.sub.63 mol %-g- 63 37 0.46 0.54 3 PVL.sub.37 mol % iPP.sub.66 mol %-g- 66 34 0.50 0.50 3 PVL.sub.34 mol % iPP.sub.76 mol %-g- 76 24 0.62 0.38 6 PVL.sub.24 mol % iPP.sub.52 mol %-g- 52 48 0.33 0.67 3 PCL.sub.48 mol % iPP.sub.53 mol %-g- 53 47 0.33 0.67 6 PCL.sub.47 mol % iPP.sub.71 mol %-g- 71 29 0.52 0.48 6 PCL.sub.29 mol % iPP.sub.73 mol %-g- 73 27 0.55 0.45 3 PCL.sub.27 mol % .sup.avalerolactone unit for PVL and caprolactone unit for PCL.

(41) TABLE-US-00002 TABLE 2 Characterisation of the copolymer by .sup.1H NMR and SEC. Mn of polyester M.sub.n.sup.a M.sub.w.sup.a .sub.M OH OH/ per grafted [kDa] [kDa] (SEC).sup.a mol %.sup.b chain.sup.b chain.sup.c i-poly(propylene- 27.8 63.3 2.3 0.9 6 N.A. co-undecenol) PP.sub.53 mol %-g- 22.9 71.0 3.1 N.A. 6 9.9 PVL.sub.47 mol % PP.sub.56 mol %-g- 21.8 69.3 3.2 N.A. 6 8.8 PVL.sub.44 mol % iPP.sub.76 mol %-g- 25.2 73.4 2.9 N.A. 6 4.9 PVL.sub.24 mol % PP.sub.53 mol %-g- 20.3 100.5 5.0 N.A. 6 11.6 PCL.sub.47 mol % iPP.sub.71 mol %-g- 20.4 89.3 4.4 N.A. 6 5.0 PCL.sub.29 mol % i-poly(propylene- 22.9 58.6 2.6 0.5 3 N.A. co-undecenol) PP.sub.52 mol %-g- 14.6 60.5 4.1 N.A. 3 17.2 PVL.sub.48 mol % PP.sub.63 mol %-g- 22.5 66.2 2.9 N.A. 3 10.4 PVL.sub.37 mol % PP.sub.66 mol %-g- 23.2 67.3 2.9 N.A. 3 9.5 PVL.sub.34 mol % PP.sub.52 mol %-g- 31.2 119.1 3.8 N.A. 3 19.4 PCL.sub.48 mol % iPP.sub.73 mol %-g- 20.6 85.7 4.2 N.A. 3 8.4 PCL.sub.27 mol % .sup.aMolar mass (kDa) and polydispersity index (.sub.M) were measured by HT-SEC in o-DCB at 150 C. (using PS standard and Mark-Houwink parameters). .sup.bAmount of pending OH groups per chain was determined by .sup.1H NMR. .sup.cMolar mass of PVL was determined by .sup.1H NMR.

(42) TABLE-US-00003 TABLE 3 Thermal properties. T.sub.c ( C.).sup.a T.sub.m ( C.).sup.a PVL or PCL PP PVL or PCL PP i-poly(propylene- N.A. 105.7 N.A. 142.3 co-undecenol) PP.sub.53 mol %-g-PVL.sub.47 mol % 10.1 109.7 51.7 143.9 PP.sub.56 mol %-g-PVL.sub.44 mol % 6.9 107.0 46.0 141.9 PP.sub.53 mol %-g-PCL.sub.47 mol % 18.0 105.1 48.9 141.3 i-poly(propylene- N.A. 110.2 N.A. 147.2 co-undecenol) PP.sub.52 mol %-g-PVL.sub.48 mol % 26.1 110.9 50.8 148.7 PP.sub.63 mol %-g-PVL.sub.37 mol % 13.3 112.9 48.4 148.1 PP.sub.66 mol %-g-PVL.sub.34 mol % 8.9 112.5 47.3 148.3 PP.sub.52 mol %-g-PCL.sub.48 mol % 20.0 113.2 47.5 148.2 .sup.aT.sub.c and T.sub.m were determined by DSC.

(43) TABLE-US-00004 TABLE 4 Mechanical properties. Young's Tensile toughness modulus (MPa).sup.a (J/m.sup.3).sup.a OH/chain.sup.b PP.sub.53 mol %-g-PCL.sub.47 mol % 660 35.1 6 PP.sub.53 mol %-g-PVL.sub.47 mol % 415 85.3 6 PP.sub.56 mol %-g-PVL.sub.44 mol % 740 21.3 6 PP.sub.53 mol %-g-PCL.sub.47 mol % 225 5.6 6 after degradation PP.sub.53 mol %-g-PVL.sub.47 mol % 145 1.9 6 after degradation PP.sub.56 mol %-g-PVL.sub.44 mol % 186 2.6 6 after degradation PP.sub.52 mol %-g-PCL.sub.48 mol % 733 6930.sup.b 3 PP.sub.52 mol %-g-PVL.sub.48 mol % 780 4.7 3 PP.sub.63 mol %-g-PVL.sub.37 mol % 787 32.1 3 PP.sub.66 mol %-g-PVL.sub.34 mol % 670 11.71 3 PP.sub.52 mol %-g-PCL.sub.48 mol % 120 0.6 3 after degradation PP.sub.52 mol %-g-PVL.sub.48 mol % 106 0.7 3 after degradation PP.sub.63 mol %-g-PVL.sub.37 mol % 115 0.4 3 after degradation PP.sub.66 mol %-g-PVL.sub.34 mol % after degradation 180 1.43 3 .sup.aYoung's moduli and tensile toughness were determined by tensile experiments. .sup.bVery ductile material, deformed to the maximum (500%) of the tensile machine without breaking.

(44) TABLE-US-00005 TABLE 5 Porosity characterisation. pore size pore size Surface distribution distribution area.sup.b adsorption.sup.a(nm) desorption.sup.a (nm) (m.sup.2/g) PP.sub.53 mol %-g-PVL.sub.47 mol % 41.0 21.0 105 PP.sub.56 mol %-g-PVL.sub.44 mol % 40.6 18.4 62 PP.sub.53 mol %-g-PCL.sub.47 mol % 22.0 12.8 121 PP.sub.52 mol %-g-PVL.sub.48 mol % 60.7 24.7 76 PP.sub.63 mol %-g-PVL.sub.37 mol % 52.2 23.4 93 PP.sub.66 mol %-g-PVL.sub.34 mol % 36 20.4 73 PP.sub.52 mol %-g-PCL.sub.48 mol % 63.6-76 33.3 90 .sup.aPore size distribution determined by Barret-Joyner-Halenda model. .sup.bSurface area determined by Brunauer-Emmet-Teller method.