Polyacrylate-based graft copolymer

Abstract

The invention relates to a polyacrylate-based graft copolymer comprising a polyacrylate backbone and polyolefin side chains grafted thereon, wherein the graft copolymer is prepared by reacting a first polymer and a second polymer, wherein the first polymer comprises recurring units having the structure (I) and optionally further recurring units having the structures (II): Formulae (I), (II) wherein R.sup.1, R.sup.3 is H or CH.sub.3 and R.sup.2 is a hydrocarbon moiety comprising 1 to 6 carbon atoms, one of R.sup.4 and R.sup.5 is H and the other one of R.sup.5 and R.sup.4 is COOR.sup.2, CN, Cl, or an aliphatic or aromatic hydrocarbon moiety optionally containing one or multiple hetero atom functionalities, wherein R.sup.2 in (I) is different from R.sup.2 in (II) and the second polymer is a functionalized polyolefin having one or multiple hydroxyl functional groups, wherein the graft copolymer is formed by transesterification of the COOR.sup.2 group of (I) or (II) with the hydroxyl functional group of the functionalized polyolefin.

Claims

1. A process for the preparation of a polyacrylate-based graft copolymer comprising a polyacrylate backbone and polyolefin side chains grafted thereon, wherein the graft copolymer is prepared by reacting a first polymer and a second polymer, wherein the first polymer comprises recurring units having the structure (I) and optionally further recurring units having the structures (II): ##STR00014## wherein R.sup.1, R.sup.3 is H or CH.sub.3 and R.sup.2 is a hydrocarbon moiety comprising 1 to 6 carbon atoms, one of R.sup.4 and R.sup.5 is H and the other one of R.sup.5 and R.sup.4 is COOR.sup.2, CN, Cl, or an aliphatic or aromatic hydrocarbon moiety optionally containing one or multiple hetero atom functionalities, wherein R.sup.2 in (I) is different from R.sup.2 in (II), and the second polymer is a functionalized polyolefin having one or multiple hydroxyl functional groups, wherein the graft copolymer is formed by transesterification of the COOR.sup.2 group of (I) or (II) with the hydroxyl functional group of the functionalized polyolefin, the process comprising the step of reacting the first polymer with the second polymer by means of transesterification.

2. The process according to claim 1, wherein the second polymer is obtained by a process comprising the steps of: (F) grafting onto the backbone of a polyolefin at least one compound comprising at least one amine-reactive group to form a grafted polyolefin and (G) reacting an alkanolamine with the grafted polyolefin before the step of reacting the first polymer and the second polymer.

3. The process according to claim 1, wherein the transesterification reaction of the polyacrylate and the functionalized polyolefin is performed by reactive melt extrusion or by a solution process.

4. The process according to claim 1, wherein (I) of the first polymer is derived from a monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isopropyl acrylate, isopropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, dimethylaminomethyl acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminomethyl methacrylate, glycidyl methacrylate, diethylene glycol diacrylate and combinations thereof.

5. The process according to claim 1, wherein (II) of the first polymer is derived from a monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isopropyl acrylate, isopropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, dimethylaminomethyl acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminomethyl methacrylate, glycidyl methacrylate, diethylene glycol diacrylate, styrene, -methylstyrene, vinyl toluene, vinyl pyridine, chlorostyrene, acrylonitrile, 2-isopropenyt-2-oxazoline, N-vinyl pyrrolidinone, vinyl acetate, vinyl chloride, dimethyl maleate, diethyl maleate, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethylitaconate, diethylitaconate, dibutylitaconate, butadiene, isoprene and combinations thereof.

6. The process according to claim 1, wherein the first polymer is a block copolymer comprising a polyacrylate block and a polystyrene block.

7. The process according to claim 1, wherein the fraction of the recurring unit (I) in the recurring units of the first polymer is at least 10%.

8. The process according to claim 1, wherein the polyolefin of the second polymer is a propylene-based polymer, an ethylene-based polymer or an ethylene-propylene rubber.

9. The process according to claim 1, wherein the second polymer has on average n functional groups per chain, wherein n is 0.5 to 5.0 as determined by .sup.1H NMR spectroscopy.

10. The process according to claim 1, wherein the second polymer is a copolymer comprising a polyolefin main chain and one or multiple functionalized short chain branches.

11. The process according to claim 10, wherein the second polymer is obtained by a process comprising the steps of: (D) copolymerizing at least one first type of olefin monomer and at least one second type of metal-pacified functionalized olefin monomer using a catalyst system to obtain a polyolefin main chain having one or multiple metal-pacified functionalized short chain branches, the catalyst system comprising: i) a metal catalyst or metal catalyst precursor comprising a metal from Group 3-10 of the lUPAC Periodic Table of elements; and ii) optionally a co-catalyst; (E) reacting the polyolefin obtained in step D) with at least one metal substituting agent to obtain a polyolefin main chain having one or multiple functionalized short chain branches, wherein the functionalized chain end comprises a hydroxyl group.

12. The process according to claim 11, wherein the at least one second type of metal-pacified functionalized olefin monomer is a compound according to Formula III: ##STR00015## wherein R.sup.6, R.sup.7 and R.sup.8 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms, and wherein R.sup.9O-ML.sub.n is a main group metal pacified hydroxyl functional group, wherein R.sup.9 is a hydrocarbyl with 1 to 16 carbon atoms; wherein M is the pacifying metal, preferably selected from the group consisting of: magnesium, calcium, boron, aluminum, gallium, bismuth, titanium, zinc, and one or more combinations thereof; wherein ligand L is independently selected from the group consisting of hydride, hydrocarbyl, halide, alkoxide, aryloxide, amide, thiolate, mercaptate, carboxylate, carbamate, salen, salan, salalen, guanidinate, porphyrin, beta-ketiminate, phenoxy-imine, phenoxy-amine, bisphenolate, trisphenolate, alkoxyamine, alkoxyether, alkoxythioether, subcarbonate and subsalicylate or combinations thereof; wherein n is 1, 2 or 3.

13. The process according to claim 1, wherein the second copolymer is a propylene-based polymer, wherein the second polymer has on average n functional groups per chain, wherein n is on average 1.0 to 4.0 as determined by .sup.1H NMR spectroscopy.

14. The process according to claim 1, wherein the second polymer is a polyolefin containing at least one functionalized chain end.

15. The process according to claim 1, wherein the second polymer is obtained by a process comprising the steps of: (A) polymerizing at least one type of olefin monomer using a catalyst system to obtain a first polyolefin containing a main group metal on at least one chain end; the catalyst system comprising i) a metal catalyst or metal catalyst precursor comprising a metal from Group 3-10 of the lUPAC Periodic Table of elements; and ii) at least one type of chain transfer agent; and iii) optionally a co-catalyst, and (B) reacting the first polyolefin containing a main group metal on at least one chain end obtained in step A) with at least one type of oxidizing agent and subsequently at least one type of metal substituting agent to obtain the polyolefin containing at least one functionalized chain end which comprises a hydroxyl group.

16. The process according to claim 1, wherein the second polymer is obtained by a process comprising the steps of: (F) grafting onto the backbone of a polyolefin at least one compound comprising at least one amine-reactive group to form a grafted polyolefin and (G) reacting an alkanolamine with the grafted polyolefin.

17. The process according to claim 1, wherein the first polymer has a number average molecular weight (M.sub.n) of 2 to 150 kg/mol.

18. The process according to claim 1, wherein the second polymer has a number average molecular weight (M.sub.n) of 1 to 300 kg/mol.

19. The process according to claim 1, wherein the molar ratio between the first polymer and the second polymer is 4:1 to 1:10.

Description

EXPERIMENTAL SECTION

(1) General Considerations. All operations were carried out in a nitrogen-filled glovebox and polymerisation reactions were performed under nitrogen atmosphere. Reagents 2,2-Azobis(2-methylpropionitrile) (AIBN, 98%), methyl acrylate (99%), butyl acrylate (99%), 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT, 98%), 1-dodecanethiol (98%) and solvents anhydrous toluene (99.8%), tetrahydrofuran (99.9%) and anhydrous dichloromethane (99.8%) were purchased from Sigma-Aldrich and used without further purification. Polymers were dried with Dean-Stark apparatus for at least 24 h before each reaction.

(2) High temperature Size Exclusion Chromatography (HT-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 data were processed using Calculations Software GPC One. The molecular weights were calculated with respect polystyrene standards.

(3) Size Exclusion Chromatography (SEC). Measurements were performed at room temperature on a Agilent Technologies 1200 series GPC system equipped with a refractive index detector. Dichloromethane (DCM) was used as an eluent at a flow rate of 0.3 mL/min. The molecular weights were calculated with respect poly(methyl methacrylate) standards.

(4) Liquid-state .sup.1H NMR. .sup.1H NMR and .sup.13C NMR spectra were recorded at room temperature or at 80 C. using a Varian Mercury Vx spectrometer operating at Larmor frequencies of 500 MHz and 100.62 MHz for .sup.1H and .sup.13C, respectively. For .sup.1H NMR experiments, the spectral width was 6402.0 Hz, acquisition time 1.998 s and the number of recorded scans equal to 64. .sup.13C NMR spectra were recorded with a spectral width of 24154.6 Hz, an acquisition time of 1.3 s, and 256 scans. The amount of OH groups in the functionalized PO was estimated using CH.sub.2OH signals area present around 3.5 ppm.

(5) Spin-Coated Film Annealing for Atomic Force Microscopy (AFM) Analysis.

(6) Different types of PS-PA and PS-PA-PP copolymers were spin-coated onto silicon wafer. To achieve self-assemble microphase separation structure of the spin-coated films. Samples are treated with annealing procedures before AFM imaging. Detailed annealing procedures have been specified in the images.

(7) Self-Assembly Morphology Characterizations by AFM

(8) AFM characterization was performed at Dimension FastScan AFM system from Bruker utilizing 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.

(9) PP/PS Blends Morphology Characterization by SEM Imaging

(10) The cross-sectional morphologies of both the PP/PS blend prepared without compatibilizer and the PP/PS blend compatibilized by PS-co-PMA-graft-PP were examined with a JEOL JSM 7800-F Field Emission Scanning Electron Microscopy (FE-SEM) at an operating voltage of 5 kV using LED detector. Before imaging, the molded samples were cryogenically fractured for the cross-sectional morphology characterization. Also both the samples were sputter-coated with gold-palladium in order to reduce the surface charging during SEM imaging.

(11) Preparation of poly(C.sub.3-co-C.sub.11OH) (Table 1, Entry 1)

(12) The propylene copolymerization experiment with 10-undecen-1-ol (entry 1, Table 1) was carried out in a stainless steel autoclave (20 L). The reactor was first washed with PMH (10 L) and vigorously stirred (500 rpm) for about 120 min at 180 C. After draining off the washing solvent, the reactor conditioning stared by applying a pre-set procedure (150 C. and three cycles of vacuum (10 mbar), nitrogen (2 bar), total time 60 min). Pentamethyl heptane PMH was added (15 L) and temperature was set at 80 C. under continuous stirring (300 rpm). Solutions of TiBA (1.0 M solution in toluene, 20.0 mmol), TiBA protected 10-undecen-1-ol (1.0 M solution in toluene, 25 mL, TiBA/C11OH=1) and MAO (30 wt % solution in toluene, 45 mmol) were added. The propylene is dosed continuously into the reactor under a stirring speed of 300 rpm until reaching full solvent saturation (propylene uptake null as measured by Bronkhorst mass flow controller) in about 90 min, 80 C. and 5 bar partial propylene pressure. Once the saturation of PMH solvent is completed, DEZ (1.0 M in hexanes, 5.0 mL diluted in about 10 mL toluene) was injected applying a 1 bar N2 overpressure, immediately followed by the injection of a catalyst solution in toluene (0.5 mg catalyst powder dissolved in about 15 mL toluene, 0.8 mol) applying a 1 bar N2 overpressure. The pressure set point is raised to match the pressure after injecting DEZ and catalyst solutions to keep the partial propylene pressure at 5 bar. After 50 minutes, the mixture was drawn off via a bottom valve in a container (equipped with a filter) containing a mixture of pure isopropanol (1.0 L) and acidified isopropanol (2.5% v/v CH3COOH, 1.0 L). After cooling down the drained suspension, the filtration was started by opening the valve of dumping vessel. The obtained solid was washed with demineralized water and dried at 60 C. in vacuo overnight (303 g). The functionalization level (OH in mol. %) was determined using .sup.1H NMR to be 0.15 mol. %. The OH content was calculated using the ratio of the triplet corresponding to the polypropylene PP-grafted 10-undecen-1-ol branch (CH.sub.2CH(CH.sub.2).sub.8CH.sub.2OH) versus the multiplet corresponding to [CH.sub.3(CH)(CH.sub.2)].sub.n of the PP backbone.

(13) This experiment was repeated by varying conditions viz. TIBA and DEZ concentration as well as 1-hexene and functionalized comonomer concentration. Results are summarized in Table 1. 1-Hexene (2 mL) was used in addition to propylene for entries 4 and 5. Entries 1, 5 and 6 were performed in a 20 L reactor instead of a 2 L reactor. Entry 6 was performed using a 3 times higher concentration of functionalized comonomer.

(14) Polymerisation of Methyl Acrylate (Table 2, Entry 1).

(15) ##STR00005##

(16) Methyl acrylate (391 mL, 4.3 mol) was purified by passing it over a column containing basic alumina. Methyl acrylate was dissolved in THF (40 wt %), the mixture was degassed using three vacuum/nitrogen cycles and was heated to 50 C. after which AIBN (82 mg, 0.5 mmol) and dodecanethiol (43 L, 0.25 mmol) were added. After one hour, solvent and unreacted monomer were removed under reduced pressure and the crude product was precipitated in cold (cooled with liquid nitrogen) methanol and filtrated. After drying in a vacuum oven (60 C.) poly(methyl acrylate) was obtained as a transparent solid. Yield: 297 g (80%), HT SEC (IR detector, o-DCB): M.sub.n=3,200 g/mol, =2.0 and SEC (RI detector, CH.sub.2Cl.sub.2): M.sub.n=10,200 g/mol, =2.1.

(17) Polymerisation of Butyl Acrylate (Table 2, Entry 2).

(18) ##STR00006##

(19) Butyl acrylate (42 mL, 0.29 mol) was purified by passing it over a column containing basic alumina. Methyl acrylate was dissolved in THF (40 wt %), the mixture was degassed using three vacuum/nitrogen cycles and was heated to 50 C. after which AIBN (82 mg, 0.5 mmol) and dodecanethiol (43 L, 0.25 mmol) were added. After one hour, solvent and unreacted monomer were removed under reduced pressure and the crude product was precipitated in cold methanol and filtrated. After drying in a vacuum oven (60 C.) poly(butyl acrylate) was obtained as a transparent gel. Yield: 32 g, (84%), HT SEC (IR detector, o-DCB): M.sub.n=9,800 g/mol, =2.4 and SEC (RI detector, CH.sub.2Cl.sub.2): M.sub.n=16,500 g/mol, =2.0.

(20) Polymerisation of Styrene (Table 2, Entry 4)

(21) ##STR00007##

(22) A mixture of styrene (50 mL, 0.43 mol) and DDMAT (0.16 g, 0.43 mmol) was degassed using three vacuum/nitrogen cycles and then was placed on a preheated reaction block at 120 C. After four hours, solvent and unreacted monomer were removed under reduced pressure and the crude product was precipitated in cold methanol. The resulting product was dried under vacuum at 70 C. to give a yellow solid (yield: 17.2 g (38%), HT SEC (IR detector, o-DCB): M.sub.n=21,000 g/mol; =1.2 and SEC (RI detector, CH.sub.2Cl.sub.2, PS standards): M.sub.n=20,300 g/mol, =1.3.

(23) This experiment (Table 2, Entry 4) was repeated by varying conditions viz. amount of used radical initiator and chain transfer agent. Further, as can be understood from Table 2, AIBN was added for Entries 6 and 7. The monomer and the CT agent used as well as the results are summarized in Table 2.

(24) Transesterification of Poly(Methyl Acrylate) with Hydroxyl-Functionalized iPP (Table 3, Entry 3).

(25) ##STR00008##

(26) Ti(OiPr).sub.4 (3.19 mg, 11.2 mol, diluted in 3 mL of toluene) was added to a solution of poly(C.sub.3-co-C.sub.11OH) (2.16 g, 50 mol in 300 ml of toluene; Table 1., Entry 1.) at 100 C. After refluxing for one hour, a solution of poly(methyl acrylate) (0.16 g, 50 mol (according to HT SEC) in 1 mL of toluene; (Table 2., Entry 1.) was added. After refluxing for 24 hours most of the solvent was removed under reduced pressure and the polymer was precipitated in cold methanol. The precipitate was mixed with THF and filtrated to remove unreacted polyacrylate. The remaining white solid was dried in a vacuum oven (60 C.). The conversion of OH groups reached 45% (based on .sup.1H NMR). HT SEC (IR detector, o-DCB): M.sub.n=42,900 g/mol, =2.1 (Table 3, Entry 3).

(27) Transesterification of Poly(Butyl Acrylate) with Hydroxyl-Functionalized iPP (Table 3, Entry 4).

(28) ##STR00009##

(29) Ti(OiPr).sub.4 (3.19 mg, 11.2 mol, diluted in 3 mL of toluene) was added to a solution of poly(C.sub.3-co-C.sub.11OH) (2.16 g, 50 mol in 300 ml of toluene; Table 1., Entry 1.) at 100 C. After refluxing for one hour, a solution of poly(butyl acrylate) (0.52 g, 50 mol; calculated according to HT SEC) in 3 mL of toluene (Table 2., Entry 2.) was added. After refluxing for 24 hours most of the solvent was removed under reduced pressure and the polymer was precipitated in cold methanol. The precipitate was mixed with THF and filtrated to remove unreacted polyacrylate. The remaining white solid was dried in a vacuum oven (60 C.). The conversion of OH groups of hydroxyl-functionalized polypropylene reached 40% (based on .sup.1H NMR). HT SEC (IR detector, o-DCB): M.sub.n=41,700 g/mol, =2.1 (Table 3, Entry 4).

(30) These experiments were repeated by varying the types and the amounts of the hydroxyl functionalized iPP and the polyacrylate and the catalyst type as shown in Table 3. The results are also summarized in Table 3.

(31) Preparation of Polystyrene-Block-Poly(Methyl Acrylate) (Table 4, Entry 4).

(32) ##STR00010##

(33) A solution of polystyrene prepared via RAFT polymerisation with DDMAT (42.0 g, 2.0 mmol, Table 2. Entry 6.), methyl acrylate (172.2 g, 2.0 mol), AIBN (32.8 mg, 0.2 mmol) and THF (275 ml) was degassed using three vacuum/nitrogen cycles and then was placed on a preheated reaction block at 70 C. After four hours, solvent and unreacted monomer were removed under reduced pressure and the crude product was precipitated in cold methanol and precipitated in dichloromethane/methanol. The resulting product was dried under vacuum at 70 C. to give a yellowish solid (yield: 34%), HT SEC (IR detector, o-DCB): M.sub.n=16,500 g/mol, =1.2; NMR: M.sub.n=17,800 g/mol).

(34) This experiment was repeated by varying the types of the polystyrene and the acrylate as shown in Table 4. The results are also summarized in Table 4.

(35) Transesterification of Polystyrene-Block-Poly(Methyl Acrylate) with Hydroxyl-Functionalized iPP (Table 5, Entry 1)

(36) ##STR00011##

(37) Ti(OiPr).sub.4 (37 L, 0.13 mmol, diluted in 3 mL of toluene) was added to a solution of poly(C.sub.3-co-C.sub.11OH) (2.9 g, 50 mol in 250 ml of toluene; Table 1., Entry 2.) at 100 C. After refluxing for one hour, a solution of polystyrene-block-poly(methyl acrylate) (4.9 g, 50 mol (according to .sup.1H NMR) in 50 mL of toluene; Table 4., Entry 1.) was added. After refluxing for 24 hours most of the solvent was removed under reduced pressure and the polymer was precipitated in cold methanol. The precipitate was dried and then unreacted polystyrene-block-poly(methyl acrylate) was removed using Soxhlet extraction with dichloromethane. The remaining pale yellow solid was dried in a vacuum oven (60 C.). The conversion of OH groups of hydroxyl-functionalized polypropylene reached 58% (93% poly(C.sub.3-co-C.sub.11OH) reacted with the block copolymer). HT SEC (IR detector, o-DCB): M.sub.n=62,600 g/mol, =2.5 (Table 5, Entry 1).

(38) Transesterification of Polystyrene-Block-Poly(Methyl Acrylate) with Hydroxyl-Functionalized iPP by Reactive Extrusion (Table 5, Entry 9)

(39) ##STR00012##

(40) Ti(OiPr).sub.4 (1.19 g, 4.2 mmol, diluted in 3 mL of toluene) was added to a solution of dry poly(C.sub.3-co-C.sub.6-co-C.sub.11OH) (8.0 g, 200 mol in 250 ml of toluene; Table 1., Entry 4.) at 100 C. After refluxing for one hour, the solvent was evaporated. Such prepared product was subsequently processed with polystyrene-block-poly(methyl acrylate) (3.30 g, 200 mol, Table 4., Entry 4) in the miniextruder at 190 C. for 10 minutes. The conversion of OH groups of hydroxyl-functionalized polypropylene reached 37% (48% poly(C.sub.3-co-C.sub.6-co-C.sub.11OH) reacted with the block copolymer). HT SEC (IR detector, o-DCB): M.sub.n=37600 g/mol, =2.8 (Table 5, Entry 9).

(41) Transesterification of Polystyrene-Block-Poly(Butyl Acrylate) with Hydroxyl Functionalized iPP (Table 5, Entry 2)

(42) ##STR00013##

(43) Ti(OiPr).sub.4 (37 L, 0.13 mmol, diluted in 3 mL of toluene) was added to a solution of poly(C.sub.3-co-C.sub.11OH) (2.9 g, 50 mol in 250 ml of toluene; Table 1., Entry 2.) at 100 C. After refluxing for one hour, a solution of polystyrene-block-poly(butyl acrylate) (3.8 g, 50 mol (according to .sup.1H NMR) in 50 mL of toluene Table 4., Entry 2.) was added. After refluxing for 24 hours most of the solvent was removed under reduced pressure and the polymer was precipitated in cold methanol. The precipitate was dried and then unreacted polystyrene-block-poly(butyl acrylate) was removed using Soxhlet extraction with dichloromethane. The remaining pale yellow solid was dried in a vacuum oven (60 C.). The conversion of OH groups of hydroxyl-functionalized polypropylene reached 56% (90% of poly(C.sub.3-co-C.sub.11OH) reacted with the block copolymer). HT SEC (IR detector, o-DCB): M.sub.n=76,200 g/mol; =2.5 (Table 5, Entry 2).

(44) This experiment was repeated by varying the types and the amounts of the hydroxyl functionalized iPP and the type of PS-b-PA and the catalyst type as shown in Table 5. The results are also summarized in Table 5.

(45) Typical procedure for the preparation of PP/PS blends. Isotactic PP (PP500P, 8.0 g) and PS (2.0 g) with antioxidant Irganox 1010 (2500 ppm) were fed into a corotating twin-screw mini-extruder at 240 C. with a screw rotation rate set at 100 rpm. The mixture was processed for 5 minutes. Afterwards the mixture was evacuated directly to a mini-injection molding machine and the obtained blends were tested in terms of their morphology and mechanical properties.

(46) Typical procedure for the preparation of PP/PS blends compatibilized by PS-b-PMA-graft-PP. Isotactic PP (PP500P, 8.0 g), PS (2.0 g), antioxidant Irganox 1010 (2500 ppm) and PS-b-PMA-g-PP (Tab 5., Entry 1.) compatibilizer (0.5 g) were fed into a corotating twin-screw mini-extruder at 240 C. with a screw rotation rate set at 100 rpm. The mixture was processed for 5 minutes. Afterwards the mixture was evacuated directly to a mini-injection molding machine and the obtained blends were tested in terms of their morphology and mechanical properties.

(47) Mechanical properties of the obtained compositions were measured as summarized in Table 6. The tensile modulus, stress at yield, elongation at break of the composition comprising the compatibilizer (Entry 3) were higher than those of the composition without the compatibilizer (Entry 2). Moreover, a much higher uniformity was obtained in the properties of the compositions comprising the compatibilizer.

(48) TABLE-US-00001 TABLE 1 Hydroxyl-functionalized polypropylenes used in transesterification of polyacrylates. OH M.sub.n OH/ [mol Entry Composition [g/mol] chain %] 1. poly(C.sub.3-co-C.sub.11OH) 43,200 2.0 1.6 0.15 2. poly(C.sub.3-co-C.sub.11OH) 57,900 2.2 1.6 0.12 3. poly(C.sub.3-co-C.sub.11OH) 58,500 2.2 1.6 0.12 4. poly(C.sub.3-co-C.sub.6-co-C.sub.11OH) 40,000 2.3 1.4 0.13 5. poly(C.sub.3-co-C.sub.6-co-C.sub.11OH) 85.500 2.0 1.6 0.08 6. poly(C.sub.3-co-C.sub.11OH) 52,600 2.1 5.1 0.41 M.sub.n and values are determined by HT SEC.

(49) TABLE-US-00002 TABLE 2 Acrylates and styrene polymerisations. Yield Entry Substrates CT agent [%] M.sub.n [g/mol] 1. methyl acrylate AIBN (0.012M) dodecanethiol (0.0025M) 80 3,200 2.0 2. butyl acrylate AIBN (0.012M) dodecanethiol (0.0025M) 87 9,800 2.4 3. styrene DDMAT (0.1% mol) 36 22,000 1.2 4. styrene DDMAT (0.1% mol) 38 21,000 1.2 5. styrene DDMAT (0.1% mol) 72 56,400 1.2 6. styrene AIBN (50 ppm) DDMAT (0.2% mol) 33.sup.b 10,800 1.3 7. styrene AIBN (100 ppm) DDMAT (0.4% mol) 41 7,000 1.3 .sup.areaction performed for 17 h; .sup.breaction performed for 4 h; M.sub.n and values determined from HT SEC

(50) TABLE-US-00003 TABLE 3 Transesterifications of polyacrylates with hydroxyl-functionalized iPP. Substrates Product Amount Amount catalyst Conversion iPP chains M.sub.n Entry iPP-co-C.sub.11OH [mol] polyacrylate [mol] substance [%].sup.b reacted [g/mol] 1. Table 1, Entry 1. 50 Table 2, Entry 1. 50 TBD (1.5 eq) 40 64 44,900 2.0 2. Table 1, Entry 1. 50 Table 2, Entry 2. 50 TBD (1.5 eq) 39 62 35,400 2.5 3. Table 1, Entry 1. 50 Table 2, Entry 1. 50 Ti(OiPr).sub.4 (1.5 eq) 45 72 42,900 2.1 4. Table 1, Entry 1. 50 Table 2, Entry 2. 50 Ti(OiPr).sub.4 (1.5 eq) 40 64 41,700 2.1 5. Table 1, Entry 1. 50 Table 2, Entry 1. 50 TMA (1 eq) 48 77 41,400 2.2 6. Table 1, Entry 1. 50 Table 2, Entry 2. 50 TMA (1 eq) 57 91 39,700 2.3 7. Table 1, Entry 3. 300 Table 2, Entry 1. 300 Ti(OiPr).sub.4 (1.5 eq) 36 58 58,100 2.3 8. Table 1, Entry 6. 50 Table 2, Entry 1. 50 TBD (15 eq) Cross- linked .sup.aequivalents per OH group in hydroxyl-functionalized iPP; .sup.bconversion of hydroxyl groups of hydroxyl-functionalized iPP determined from .sup.1H NMR; M.sub.n and values determined from HT SEC

(51) TABLE-US-00004 TABLE 4 Block copolymers preparation. Substrates Product Amount Amount Yield M.sub.n Entry polystyrene [mmol] acrylate [mol] Catalyst [%] [g/mol] 1. Table 2. Entry 3. 0.41 methyl acrylate 0.41 AIBN (100 ppm) 96 12,000 2.3 2. Table 2. Entry 4. 0.41 butyl acrylate 0.41 AIBN (100 ppm) 50 33,300 1.8 3. Table 2. Entry 5. 0.41 methyl acrylate 0.41 AIBN (100 ppm) 41 37,000 1.6 4. Table 2. Entry 6. 2.1 methyl acrylate 2.1 AIBN (100 ppm) 34 16,500 1.2 5. Table 2. Entry 7. 0.41 methyl acrylate 0.41 AIBN (100 ppm) 34 6,400 1.2 M.sub.n and values determined from HT SEC;

(52) TABLE-US-00005 TABLE 5 Terpolymers preparations. Product Substrates OH iPP Amount Amount conversion conversion M.sub.n Entry iPP-co-C.sub.11OH [mol] PS-b-PA [mol] Catalyst [%].sup.b [%].sup.c [g/mol] 1. Table 1. Entry 2. 50 Table 4. Entry 1. 50 Ti(OiPr).sub.4 (1.5 eq) 58 93 62,600 2.5 2. Table 1. Entry 2. 50 Table 4. Entry 2. 50 Ti(OiPr).sub.4 (1.5 eq) 56 90 76,200 2.5 3. Table 1. Entry 3. 300 Table 4. Entry 3. 300 Ti(OiPr).sub.4 (1.5 eq) 49 78 56,800 2.3 4. Table 1. Entry 4. 50 Table 4. Entry 1. 150 TMA (1.5 eq) 63 88 46,200 2.1 5. Table 1. Entry 4. 50 Table 4. Entry 4. 150 Ti(OiPr).sub.4 (1.5 eq) 69 97 43,700 2.4 6. Table 1. Entry 5. 300 Table 4. Entry 2. 300 Ti(OiPr).sub.4 (1.5 eq) 59 94 65,200 2.5 7. Table 1. Entry 6. 50 Table 4. Entry 1. 50 Ti(OiPr).sub.4 (15 eq) Cross-linked n.a. n.a. 8. Table 1. Entry 5. 300 Table 4. Entry 1. 300 Ti(OiPr).sub.4 (1.5 eq) 58 93 62,300 2.7 9 Table 1. Entry 4. 200 Table 4. Entry 4. 200 Ti(OiPr).sub.4 (15 eq) 37 48 37,600 2.8 .sup.aequivalents per OH group in hydroxyl-functionalized iPP; .sup.bconversion of hydroxyl groups of hydroxyl-functionalized iPP determined from .sup.1H NMR; .sup.cpercentage of iPP reacted with styrene-acrylate block-copolymer; M.sub.n and values determined from HT SEC d) determined from .sup.1HNMR;

(53) TABLE-US-00006 TABLE 6 Tensile test results of PP500, PP500P/PS blend and PP500P/PS blend compatibilised compatibilized by Tab 5, Entry 1. Tensile Stress at modulus yield Elongation at Entry Composition [MPa] [MPa] break [%] 1. PP500P 1428.97 35.86 320.18 99.60 0.83 20.60 2. PP500P + PS 2204.40 45.82 135.14 119.64 0.93 16.59 3. PP500P + PS + 2266.73 46.53 135.33 compatibiliser 59.24 0.14 5.96

(54) FIGS. 1-4 show AFM images of spin-coated copolymer samples.

(55) FIG. 5 shows SEM images exhibiting morphology of PP500/PS blend and PP500/PS blend compatibilised by (Table 5, Entry 1.) Red arrow indicates the PS domains visualized in the PP matrix.