Compatibilised polyolefin and polycarbonate composition

Abstract

The present invention relates to a composition comprising a polyolefin, polycarbonate and a compatibiliser, articles made therefrom and the use of a graft or block copolymer as a compatibiliser.

Claims

1. A composition comprising a polyolefin, polycarbonate and a compatibiliser, wherein said compatibiliser is a block copolymer comprising a polyolefin part and a polyester part, said polyester part having an average M/F ratio 2 and 25, wherein M is the number of backbone carbon atoms in the polyester not including the carbonyl carbons and F is the number of ester groups in the polyester, wherein the compatibiliser is a BAB type block copolymer with A representing polyolefin and B representing polyester.

2. The composition of claim 1, wherein the polyester part has an average M/F ratio 2 and 10.

3. The composition of claim 1, wherein the amount of polyolefin excluding the polyolefin part of the compatibiliser is from 50-90 wt. % on the basis of the total amount of the composition or the amount of polycarbonate is from 50-90 wt. % on the basis of the total amount of the composition.

4. The composition of claim 1, wherein the amount of compatibiliser is from 0.1-10 wt. %, on the basis of the total amount of the composition.

5. The composition of claim 1, wherein the polyolefin of the composition is: a propylene homopolymer, a propylene--olefin random copolymer, a propylene--olefin block copolymer, a hetero-phasic polypropylene copolymer comprising a matrix phase and a disperse phase, the matrix phase consisting of a propylene homopolymer and/or a propylene copolymer with up to 3 wt. % of ethylene and/or at least one C.sub.4-C.sub.8 -olefin, the wt. % being based on the matrix phase, and the disperse phase consisting of an ethylene-C.sub.3-C.sub.8 -olefin copolymer, or a mixture of any of the foregoing polypropylenes.

6. The composition of claim 1, wherein the polyolefin of the composition is a very low density polyethylene, linear low density polyethylene, low density polyethylene, high density polyethylene or a mixture of any of the foregoing polyethylenes.

7. The composition of claim 1, wherein the compatibiliser has a weight average molecular weight of from 1,000 to 250,000 g/mol.

8. The composition of claim 1, wherein in the compatibiliser the polyester is selected from one or more selected from the group consisting of -butyrolactone, glycolide, L-lactide, -caprolactone, cyclic butylene adipate and cyclic ethylene brassylate.

9. The composition of claim 1, wherein the polyolefin part of the compatibiliser is a propylene homopolymer block.

10. An article comprising the composition of claim 1.

11. The article of claim 10, said article being selected from the group consisting of automotive interior articles, automotive exterior articles, household appliances, pipes, films, sheets.

12. The composition of claim 2, wherein the polyester has an average M/F ratio 3 and 7.

13. The composition of claim 4, wherein the amount of compatibiliser is from 3-8 wt. % on the basis of the sum of the amount of polypropylene and polyethylene.

14. The composition of claim 5, wherein the propylene--olefin random copolymer comprises a propylene ethylene or a propylene C.sub.4-C.sub.8 -olefin random copolymer.

15. The composition of claim 1, wherein the polyolefin part of the compatibiliser is a propylene copolymer block containing at least 90 wt. % of polypropylene, on the basis of the weight of the polypropylene block.

16. A composition comprising: a very low density polyethylene, linear low density polyethylene, low density polyethylene, or a mixture of any of the foregoing polyethylenes, polycarbonate, and a compatibiliser, wherein said compatibiliser is a block copolymer comprising a polyolefin part comprising an ethylene copolymer containing at least 90 wt. % of ethylene on the basis of the weight of the polyethylene block, and a polyester part having an average M/F ratio 2 and 25, wherein M is the number of backbone carbon atoms in the polyester not including the carbonyl carbons and F is the number of ester groups in the polyester.

Description

EXAMPLES

(1) Materials

(2) -caprolactone (CL) (97%, Sigma-Aldrich) and ethylene brassylate (>95%, Sigma-Aldrich) were dried over CaH.sub.2 and distilled under reduced pressure. Toluene (Sigma-Aldrich) was dried using an MBraun-SPS-800 purification column system.

(3) Measurement Methods

(4) Conversion of reactions was determined by NMR:

(5) .sup.1H NMR analysis (.sup.1H-NMR) carried out at 80-110 C. using deuterated tetrachloroethene (TCE-d.sub.2) as the solvent and recorded in 5 mm tubes on a Varian Mercury spectrometer operating at frequencies of 400 MHz. Chemical shifts in ppm versus tetramethylsilane were determined by reference to the residual solvent.

(6) M.sub.n, M.sub.w and the polydispersity index (PDI, .sub.M) were determined as follows by size exclusion chromatography:

(7) For Copolymers Comprising Polyethylene:

(8) Size exclusion chromatography (SEC) was performed at 160 C. on a Polymer Laboratories PLXT-20 Rapid GPC Polymer Analysis System (refractive index detector and viscosity detector) with 3 PLgel Olexis (3007.5 mm, Polymer Laboratories) columns in series. 1,2,4-trichlorobenzene (TCB) was used as eluent at a flow rate of 1 mL.Math.min.sup.1. The molecular weights were calculated with respect to polyethylene standards (Polymer Laboratories). A Polymer Laboratories PL XT-220 robotic sample handling system was used as autosampler. The SEC-data were processed using Cirrus software from Agilent.

(9) For Copolymers Comprising Polypropylene:

(10) 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 (oDCB) was used as an eluent at a flow rate of 1 mL/min. The SEC-data were processed using Calculations Software GPC One.

(11) Melting (T.sub.m) and crystallization (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 210 C. The transitions were deduced from the second heating and cooling curves.

(12) Typical Procedure for the Synthesis of Hydroxyl End-Capped Polyethylene:

(13) Polymerisation reactions were carried out in stainless steel Bchi reactors (300 mL). Prior to the polymerisation, the reactor was dried in vacuo at 40 C. and flushed with dinitrogen. PMH (90 mL) and MAO solution were added and stirred at 50 rpm for 20-30 min. TIBA and/or DEZ were added, the solution was saturated with ethylene and stirred for 10 min. In a glove box, the catalyst was dissolved in toluene (c.a. 3 mL) and transferred into the reactor. The reactor was then pressurized to the desired pressure with ethylene and the pressure was maintained for a predefined time. At the end of polymerisation, the ethylene feed was stopped and after releasing the residual ethylene pressure, synthetic air was injected through a gas injection tube and the suspension was maintained under constant oxygen pressure (6 bars) at 60 C. for 2 h with rigorous stirring (600 rpm) before quenching with 300 mL of acidified methanol (10% concentrated HCl) to isolate the functionalized polyethylene. The resulting white powder was then filtered, washed with methanol and dried at 60 C. in vacuo overnight.

(14) Synthesis of Aluminum-Salen Complex 1:

(15) N,N-bis(salicylidene)ethylenediamine (2.0 g, 7.5 mmol) was suspended in toluene (30 mL) under N.sub.2 flow. Subsequently, Al(CH.sub.3).sub.3 (2M solution in toluene, 3.75 mL, 7.5 mmol) was added via syringe and the mixture was stirred at room temperature. The thus obtained solution was concentrated to half the original volume and pale yellow needles of Al-salen complex 1 were isolated with a yield of 93%.

(16) Synthesis of Aluminum-Salen Complex 2:

(17) N,N-bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (2.0 g, 5.7 mmol) was suspended in toluene (30 mL) under N.sub.2 flow. Subsequently, Al(CH.sub.3).sub.3 (2 M solution in toluene, 2.85 mL, 5.7 mmol) was added via syringe and the mixture was stirred at room temperature. The thus obtained solution was concentrated to half the original volume and pale yellow needles of Al-salen complex 2 were isolated with a yield of 90%.

(18) FIG. 1 shows:

(19) 1: Al-salen complex 1, 2: Al-salen complex 2 and 3: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD).

(20) Typical Procedure for Synthesis of PE-Block-PCL Copolymers Via ROP:

(21) A glass crimp cap vial was charged with toluene (1.5 mL), -caprolactone (CL, 4.5 mmol), hydroxyl end-capped PE (13 mg, 8.7 mol) and Al-salen complex 1 or 2 (8.7 mol). All manipulations were carried out in the glovebox. Then, the mixture was removed from the glovebox and stirred in an oil bath at 100 C. The progress of the reaction was followed by .sup.1H NMR spectroscopy by taking aliquots at set time intervals. The synthesized copolymer was cooled to room temperature and quenched using acidified methanol, isolated and dried in vacuum at room temperature for 18 h. Results are shown in Table 1 below. The average M/F ratio for PCL may thereby be 5.

(22) Typical Procedure for the Synthesis of LLDPE Comprising an LLDPE Main Chain with Randomly Distributed Hydroxyl-Functionalized Short Chain Branches:

(23) Copolymerisation reactions of ethylene/10-undecen-1-ol were carried out in stainless steel Bchi reactors (300 mL). Prior to the polymerisation, the reactor was dried in vacuo at 40 C. and flushed with dinitrogen. Pentamethylheptane (PMH) solvent (90 mL) was introduced followed by TIBA and the functional monomer under an inert atmosphere. The resulting solution was stirred for 15-20 min followed by the addition of calculated amount of cocatalyst under dinitrogen atmosphere. The solution was saturated with ethylene and stirred for 10 min. The polymerisation reaction was started by the addition of the catalyst to the reactor. The reactor was then pressurized to the desired pressure with ethylene and the pressure was maintained for a predefined time. The ethylene feed was stopped and the resulting mixture was quenched in acidified methanol, filtered and dried under reduced pressure at 60 C. for 24 h.

(24) TABLE-US-00001 TABLE 1 Ring-opening polymerisation of CL affording block copolymers. time T M.sub.n.sup.a entry CL/cat/in [h] [ C.] [kg/mol] .sub.M.sup.a CL conv..sup.b Catalyst: Al-salen complex 1 1 1000/1/1 5 100 22520 1.8 97 2 1000/1/1* 5 100 15450 1.7 98 Catalyst: Al-salen complex 2 3 1000/1/1 5 100 30110 1.6 99 4 1000/1/1 0.5 100 9940 1.9 95 5 1000/1/1 1 100 18380 1.7 97 6 1000/1/1* 0.5 100 46700 1.7 95 7 1000/1/1* 1 100 51000 1.6 95 8 1000/1/1 0.5 80 2450 1.8 95 9 1000/1/1 1 80 19200 1.7 97 Conditions of ROP: polymerisations mediated by catalyst 1, catalyst 2 and hydroxyl functionalized linear PE with M.sub.n = 2230, .sub.M = 2.1 .sup.bmolecular weight and polydispersity determined by HT-SEC in TCB at 160 C.; .sup.bconversion of the lactones was estimated based on .sup.1HNMR analysis. *before the monomer was added the Al-salen complexes 1 or 2 were activated with the initiator in toluene for 12 h at 100 C.
Typical Procedure for Synthesis of LLDPE-Graft-PCL Copolymers Via ROP:

(25) A glass crimp cap vial was charged with -caprolactone (4.8 mmol) and Al-salen complex 2 (1.68 mg, 5 mol), LLDPE comprising a LLDPE main chain with randomly distributed hydroxyl-functionalized short chain branches (44.1 mg, 5 mol) and toluene (1.50 g, 16.3 mmol). All manipulations were carried out in the glovebox. Then, the mixture was removed from the glovebox and stirred in an oil bath at 100 C. The progress of the reaction was followed by .sup.1H NMR spectroscopy by taking aliquots at set time intervals. The synthesized copolymer was cooled to room temperature and quenched using acidified methanol, isolated and dried in vacuum at room temperature for 18 h. Results are shown in Table 2 below. The average M/F ratio for PCL may thereby be 5.

(26) Typical Procedure for Randomly Hydroxyl-Functionalized HDPE:

(27) A mixture of cis-cyclooctene (5 g, 45.5 mmol) and 5-hydroxy-cis-cyclooctene (172 mg, 1.36 mmol), 2.sup.nd generation Grubbs catalyst (19.3 mg, 22.7 mol) and toluene (10.0 mL) were stirred at room temperature for 24 h. The manipulations were carried out in the glovebox. Ethyl vinyl ether (1.7 mg, 22.7 mol) was added to quench the polymerisation after which the polymer was precipitated in acidified methanol. The unsaturated polymers were redissolved in toluene and transferred to a 300 mL stainless steel Bchi reactor. Subsequently, an appropriate amount of Wilkinson's catalyst dissolved in a small amount of toluene (2 mL) was added via syringe and the mixture was stirred for 48 h at 90 C. under the H.sub.2 (20 bar). Afterwards, the reaction mixture was quenched in acidified methanol, filtered and purified by re-precipitation in methanol. The saturated polymer, obtained with the yield of 94%, was dried under reduced pressure at 80 C. for 24 h.

(28) Typical Procedure for Synthesis of HDPE-Graft-PCL Copolymers Via ROP:

(29) A glass crimp cap vial was charged with -CL (4.8 mmol) and Al-salen catalyst 1 (3 mg, 9.7 mol), randomly hydroxyl-functionalized HDPE (70 mg, 9.7 mol) and toluene (1.50 g, 16.3 mmol). All manipulations were carried out in the glovebox. Then, the mixture was removed from the glovebox and stirred in an oil bath at 100 C. The progress of the reaction was followed by .sup.1H NMR spectroscopy by taking aliquots at set time intervals. The synthesized copolymer was cooled to room temperature and quenched using acidified methanol, isolated and dried in vacuum at room temperature for 18 h. Results are shown in Table 2 below. The average M/F ratio for PCL may thereby be 5.

(30) TABLE-US-00002 TABLE 2 Ring-opening polymerisation of CL affording HDPE-graft-PCL and LLDPE-graft-PCL copolymers. time T M.sub.n.sup.c entry CL/cat/in [h] [ C.] [kg/mol] .sub.M.sup.c CL conv..sup.d Catalyst: Al-salen complex 2 1.sup.a 1000/1/1 2 100 24800 2.1 97 2.sup.a 500/1/1 2 100 85900 2.3 94 3.sup.a 250/1/1 2 100 20700 2.8 90 4.sup.b 1000/1/1 2 100 17070 2.5 94 5.sup.b 500/1/1 2 100 15400 2.7 95 6.sup.b 250/1/1 2 100 12070 2.5 99 Catalyst 3: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) 7.sup.a 500/1/1 24 100 46600 2.1 84 8.sup.a 200/1/1 24 100 21900 2.2 96 15.sup.a 100/1/1 24 100 15500 2.3 96 .sup.aConditions of ROP: polymerisations mediated by Al-salen complex 2 or TBD and randomly hydroxyl-functionalized HDPE with M.sub.n = 9500 .sub.M = 2.4 M.sub.n = 9500 .sub.M = 2.4. .sup.bpolymerisations mediated by Al-salen complex 2 and LLDPE comprising a LLDPE main chain with randomly distributed hydroxyl-functionalized short chain branches with M.sub.n = 9200 .sub.M = 2.1 .sup.cMolecular weight and polydispersity determined by HT-SEC in TCB at 160 C.; .sup.dConversion of the lactones was estimated based on .sup.1HNMR analysis.
Typical Procedure for Synthesis of PE-Graft-PCL Copolymers Via Reactive Extrusion:

(31) The preparation was carried out in a micro compounder MC15 ml from Xplore equipped with co-rotating screws, a barrel with three 3 temperature zones and a nitrogen purge at 150 C. (three temperature zones set to 150 C.) with a screw RPM setting at 100. To form N-(2-hydroxyethyl)succinimide attached to the PE backbone maleic anhydride (MAH) functionalized HDPE (Yparex OH07, 10 g, functionalized with 1.5 wt. % of MAH, MRI=18 g/10 min, M.sub.n=12.6 kg/mol, M.sub.w=40.2 kg/mol, =3.2) with Irganox 1010 (supplied by BASF, tetrakis [Methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2250 ppm) was feed into the extruder and after a few minutes ethanolamine (0.28 g, 4.6 mmol) was added via syringe. The mixture was processed and then the extruder chamber was evacuated. The so obtained hydroxyl functionalized polyethylene was purified by dissolution in m-xylene at 120 C. and precipitated in a cold acetone. The copolymer was dried in a vacuum oven for 48 h at room temperature. Subsequently hydroxyl-functionalized PE (8.0 g, M.sub.n=12.6 kg/mol =3.2) and PCL (2.0 g, M.sub.n=25.6 kg/mol, =1.3) were feed into a twin-screw micro compounder MC15 ml from Xplore equipped with co-rotating screws, a barrel with three 3 temperature zones and a nitrogen purge at 150 C., 160 C., 180 C., respectively a screw RPM setting at 100. The polymers were premixed for 5 minutes. Then the catalyst Sn(Oct).sub.2 (0.19 g, 0.5 mmol) was added and the mixture was stirred in the extruder for 2 minutes. After this time the extruder was evacuated. The copolymer was purified by dissolution in m-xylene at 120 C. and precipitation in a cold acetone. The copolymer was dried in a vacuum oven for 48 h at room temperature. The average M/F ratio for PCL may thereby be 5.

(32) Typical Procedure for Synthesis of PP-Graft-PCL or PP-Graft-PEB Copolymers in Solution or Via Reactive Extrusion:

(33) The preparation was carried out in solution or in a twin-screw micro compounder MC15 ml from Xplore. The micro compounder was equipped with co-rotating screws, a barrel with three 3 temperature zones and a nitrogen purge at 160 C., 180 C., 190 C., respectively with a screw RPM setting at 100. To form N-(2-hydroxyethyl) succinimide attached to the PP backbone maleic anhydride (MAH) functionalized PP (polypropylene homopolymer functionalized with between 0.5 and 1 wt. % of MAH, commercially available under the name Exxelor PO1020) with Irganox 1010 (supplied by BASF, tetrakis [Methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionate] methane, 2250 ppm) was feed into the extruder and after a few minutes ethanolamine (0.28 g, 4.6 mmol) was added via syringe. The mixture was processed and then the extruder chamber was evacuated. The so obtained hydroxyl functionalized polypropylene was purified by dissolution in m-xylene at 120 C. and precipitated in a cold acetone. The copolymer was dried in a vacuum oven for 48 h at room temperature. Subsequently hydroxyl-functionalized PP and PCL or PEB in amounts indicated in Table 3 below were added to 400 ml of m-xylene to form a solution or feed into extruder with the temperature of the barrel zones set at 180 C. (three temperature zones set at 180 C.), and a screw RPM setting at 100. The polymers were premixed for 5 minutes. Then the catalyst Sn(Oct).sub.2 was added in the amount indicated in Table 3 below and the mixture was stirred in the extruder for reaction times of 2 or 5 minutes as indicated in Table 3 below. After this time the extruder was evacuated. The copolymer was purified by dissolution in m-xylene at 120 C. and precipitation in a cold acetone. The copolymer was dried in a vacuum oven for 48 h at room temperature. The average M/F ratio for PCL may thereby be 5 and the average M/F ratio for PEB may be 6.5.

(34) TABLE-US-00003 TABLE 3 PP-graft-PCL or PP-graft-PEB copolymers prepared in Solution or via reactive extrusion. PP-MAH PP-OH Polyesters Copolymers M.sub.n M.sub.n M.sub.w M.sub.n M.sub.w M.sub.n [kg .Math. M.sub.w [kg .Math. [kg .Math. Amout [kg .Math. [kg .Math. Amout [kg .Math. M.sub.w Catalyst Temp. Entry mol.sup.1] [kg .Math. mol.sup.1] mol.sup.1] mol.sup.1] [g] mol.sup.1] mol.sup.1] [g] mol.sup.1] [kg .Math. mol.sup.1] Time [%] [ C.] PP- 22.0 97.7 17.1 50.2 8 12.4 26.0 4 46.7 116.8 20 h 0.5% 120 PCL/A (reaction 0.06 g in Sn(Oct).sub.2 solution) PP- 22.0 97.7 36.6 117.9 6 12.4 26.0 3 29.6 132.3 premixed 0.5% 180 PCL/B 5 min 0.045 g reaction Sn(Oct).sub.2 2 min PP- 22.0 97.7 34.5 103.9 8 12.4 26.0 4 32.7 111.9 6 h 0.5% 120 PCL/C (reaction 0.06 g in Sn(Oct).sub.2 solution) PP- 22.0 97.7 36.6 117.9 6 20.1 45.9 3 42.7 162.5 premixed 0.5% 180 PCL/D 5 min 0.045 g reaction Sn(Oct).sub.2 2 min PP- 22.0 97.7 36.6 117.9 6 20.1 45.9 3 34.2 166.3 premixed 0.5% 180 PCL/E 5 min 0.045 g reaction Sn(Oct).sub.2 5 min PP- 22.0 97.7 36.6 117.9 6 20.1 45.9 3 47.2 183.9 premixed 1% 180 PCL/F 5 min 0.09 g reaction Sn(Oct).sub.2 5 min PP- 22.0 97.7 28.8 104.6 6 9.7 24.5 3 22.5 122.0 premixed 1% 180 PEB/A 5 min 0.09 g reaction Sn(Oct).sub.2 5 min PP- 22.0 97.7 28.8 104.6 6 28.2 75.6 3 28.4 113.0 premixed 1% 180 PEB/B 5 min 0.09 g reaction Sn(Oct).sub.2 5 min PP- 9.6 36.6 15.4 46.1 6 28.2 75.6 3 23.1 110.4 premixed 1% 180 PEB/C 5 min 0.09 g reaction Sn(Oct).sub.2 5 min
Typical Procedure for the Preparation of the PP/PC Blends:

(35) Polypropylene and polycarbonate (PC) according to Table 4 were fed into the extruder chamber. The mixture was processed for 2 or 5 minutes as indicated in Table 4 in a twin-screw micro compounder MC15 ml from Xplore. The micro compounder was equipped with co-rotating screws, a barrel with three 3 temperature zones and a nitrogen purge at 240 C. (three temperature zones set at 240 C.) with a screw rotation rate of 100 rpm. Afterwards the mixture was evacuated directly to a mini-injection moulding machine to prepare samples for morphology analysis.

(36) For each blend of the blends indicated in Table 4 10 gr samples were prepared with the indicated PP/PC ration and the amount of compatibiliser (comp.) indicated in each case (0.5 g) was added on top to each sample to get 10.5 g of each compatibilised blend.

(37) Both for PP-graft-PCL and PP-graft-PEB used as compatibilisers for PP/PC blends SEM pictures and analysis of samples of the blends listed in Table 4 show improved compatibilisation compared to corresponding non-compatibilised blends, especially for example smaller and/or better dispersed domain of the dispersed phase and/or optionally an increased adhesion between the two different polymer phases.

(38) TABLE-US-00004 TABLE 4 PP/PC blends prepared using PP-graft-PCL or PP-graft-PEB copolymers as compatibilisers. MATERIALS FOR COMPATYIBILIZERS POLYPROPYLENE PP-graft-OH POLYESTERS COPOLYMERS BLENDS M.sub.n M.sub.w M.sub.n M.sub.w M.sub.n M.sub.w PP/ comp. time [kg .Math. mol.sup.1] [kg .Math. mol.sup.1] [kg .Math. mol.sup.1] [kg .Math. mol.sup.1] [kg .Math. mol.sup.1] [kg .Math. mol.sup.1] PP PC PC [g] [min] PP- 28.8 104.6 28.2 75.6 28.4 113.0 PP500P PC105 80/20 0.5 5 PEB/B PP- 15.4 46.1 28.2 75.6 23.1 110.4 PP500P PC105 80/20 0.5 5 PEB/C PP- 28.8 104.6 28.2 75.6 28.4 113.0 PP531P PC105 80/20 0.5 5 PEB/B PP- 15.4 46.1 28.2 75.6 23.1 110.4 PP531P PC105 80/20 0.5 5 PEB/C PP- 28.8 104.6 28.2 75.6 28.4 113.0 PP531P PC175 80/20 0.5 5 PEB/B PP- 15.4 46.1 28.2 75.6 23.1 110.4 PP531P PC175 80/20 0.5 5 PEB/C PP- 17.1 50.2 12.4 26.0 30.1 193.8 PP500P PC105 80/20 0.5 5 PCL/A PP- 17.1 50.2 12.4 26.0 30.1 193.8 PP531P PC105 80/20 0.5 5 PCL/A PP- 17.1 50.2 12.4 26.0 30.1 193.8 PP531P PC105 80/20 0.5 2 PCL/A

(39) SEM analysis of the freeze fractured samples were performed using HITACHI SU8010 apparatus equipped with cold cathode field-emission source. The samples were sputter coated using Cressington Sputter Coater 108Auto with Au.

(40) Based on the SEM pictures and analysis, one can also see that the compatibilisers according to the invention with higher M/F values higher than found for PCL, especially for example PEB based polymer compatibilisers according, to the invention may thereby also display further improved adhesion between the two different compatibilised phases, even when compared to compatibilisers according to the invention with lower M/F values, especially for example PCL based polymer compatibilisers according to the invention.

(41) Typical Procedure for Synthesis of PE-Graft-PCL Copolymers Via Transesterification:

(42) The experiments were carried out in a twin-screw mini-extruder MC15 ml from Xplore at 150 C. with a screw RPM setting at 100. To form N-(2-hydroxyethyl)succinimide attached to the PE backbone (hydroxyl functionalized PE), maleic anhydride functionalized HDPE (Yparex OH07, 10 g, Mn 12600, g/mol, =3.2, MFR 18 g/10 min at 200 C./5 kg with 1.5 wt.-% maleic anhydride) with Irganox B225 (2500 ppm, from BASF, blend of Irganox 1010 and tris(2,4-ditert-butylphenyl) phosphite) was fed into the extruder and after a few minutes ethanolamine (0.28 g, 4.6 mmol) was added via syringe. The mixture was processed and then the extruder chamber was evacuated. The hydroxyl functionalized polyethylene was purified by dissolution in m-xylene at 120 C. and precipitated in a cold acetone. Subsequently, hydroxyl-functionalized PE (8.0 g, M.sub.n=12.6 kg/mol, =3.2) and PCL (2.0 g, M.sub.n=25.6 kg/mol, =1.3) were fed into a corotating twin screw mini extruder MC15 ml from Xplore at 150 C. with a screw RPM setting at 100. The polymers were premixed for 5 minutes. Then the catalyst Sn(Oct).sub.2 (0.19 g, 0.5 mmol) was added and the mixture was stirred in the extruder for 2 minutes. After this time the extruder was evacuated. The copolymer was purified by dissolution in m-xylene at 120 C. and precipitation in a cold acetone. The copolymer was dried in a vacuum oven for 48 h at room temperature. The average M/F ratio for PCL may thereby be 5.

(43) Typical Procedure for Preparation of LDPE/PC Blends:

(44) 8.0 g of LDPE (LDPE2801, MFR=0.55 g/10 min at 190 C./2.16 kg) and 2.0 g, PC (PC115, MFR=15 g/10 min at 300 C./1.2 kg) were mixed in the mini-extruder chamber (MC15 ml from Xplore). The mixture was processed at 230 C. for 5 minutes with a screw rotation rate set at 100 rpm. The weight ratio of LDPE to PC was 80/20. The blends were investigated in terms of the morphology, mechanical properties and surface properties.

(45) Typical Procedure for Preparation of LDPE/PC Blends Compatibilized by HDPE-Graft-PCL Copolymer:

(46) 8.0 g of LDPE (LDPE2801, MFR=0.55 g/10 min at 190 C./2.16 kg), 2 g of PC (PC115, MFR=15 g/10 min at 300 C./1.2 kg), and 0.5 g of HDPE-block-PCL were mixed in the mini-extruder chamber (MC15 ml from Xplore). The mixture was processed at 230 C. for 5 minutes with a screw rotation rate set at 100 rpm at a weight ratio of LDPE/PC/comaptibilizer 80/20/5, respectively. The blends were investigated in terms of the morphology, mechanical properties and surface properties.

(47) Typical Procedure for Preparation of HDPE/PC Blends:

(48) 8.0 g of HDPE (HDPE CC253, MFR=1.8 g/10 min at 190 C./2.16 kg) and 2.0 g, PC (PC115, MFR=15 g/10 min at 300 C./1.2 kg) were mixed in the mini-extruder chamber (MC15 ml from Xplore). The mixture was processed at 230 C. for 5 minutes with a screw rotation rate set at 100 rpm. The weight ratio of HDPE to PC was 80/20. The blends were investigated in terms of the morphology, mechanical properties and surface properties.

(49) Typical Procedure for Preparation of HDPE/PC Blends Compatibilized by HDPE-Graft-PCL Copolymer:

(50) 8.0 g of HDPE (HDPE CC253, MFR=1.8 g/10 min at 190 C./2.16 kg), 2 g of PC (PC115, MFR=15 g/10 min at 300 C./1.2 kg), and 0.5 g of HDPE-block-PCL were mixed in the mini-extruder chamber (MC15 ml from Xplore). The mixture was processed at 230 C. for 5 minutes with a screw rotation rate set at 100 rpm at a weight ratio of HDPE/PC/comaptibilizer 80/20/5, respectively. The blends were investigated in terms of the morphology, mechanical properties and surface properties.

(51) TABLE-US-00005 TABLE 5 PE/PC blends prepared using HDPE-graft-PCL copolymers prepared by ROP and transesterification as compatibilisers. PE/PC Izod impact weight .sub.max.sup.c .sub.at break.sup.d strength .sup.e Entry ratio compatibilizer [MPa] [%] [kJ/m.sup.2] [] LDPE2501 100/0 19.49 1.53 40.9 18.4 31.9 0.4 LDPE2501/PC115 80/20 25.53 0.42 51.0 4.5 51.0 9.5 LDPE2501/PC115 80/20 HDPE-graft-PCL.sup.a 25.71 0.73 46.1 2.1 60.0 2.0 LDPE2501/PC115 80/20 HDPE-graft-PCL.sup.b 25.40 0.54 44.8 3.3 70.6 7.6 LDPE2501/PC115 50/50 28.56 0.79 25.6 4.9 46.1 2.6 LDPE2501/PC115 50/50 HDPE-graft-PCL.sup.a 30.81 0.34 21.7 6.3 82.3 12.0 LDPE2501/PC115 20/80 34.90 1.54 6.3 0.4 107.9 11.9 LDPE2501/PC115 20/80 HDPE-graft-PCL.sup.a 49.92 0.40 5.6 0.3 103.6 8.7 LDPE2501/PC115 20/80 HDPE-graft-PCL.sup.b 41.01 1.51 11.9 1.5 127.1 4.8 LDPE2801 100/0 25.1 1.3 55.9 14.5 42.13 0.03 92.6 0.5 LDPE2801/PC115 80/20 26.1 2.6 38.6 3.9 48.5 19.3 93.8 0.2 LDPE2801/PC115 80/20 HDPE-graft-PCL.sup.a 27.3 0.2 51.2 3.4 55.9 12.1 90.8 1.3 LDPE2801/PC115 80/20 HDPE-graft-PCL.sup.b 27.8 0.2 51.8 2.5 54.5 19.9 87.6 1.8 LDPE2801/PC105 80/20 22.12 0.26 31.6 1.7 47.4 6.2 LDPE2801/PC105 80/20 HDPE-graft-PCL.sup.a 26.44 0.60 27.5 8.7 51.0 0.8 LDPE2801/PC105 80/20 HDPE-graft-PCL.sup.b 28.01 1.02 32.6 7.3 65.2 3.7 HDPE CC253 100/0 30.4 0.8 172.1 43.7 84.4 4.4 97.2 1.7 HDPE CC253/PC115 80/20 38.7 0.4 29.4 1.4 80.4 9.3 84.3 0.2 HDPE CC253/PC115 80/20 HDPE-graft-PCL.sup.a 33.5 1.6 148.8 8.4 71.1 9.1 83.4 0.1 HDPE CC253/PC115 80/20 HDPE-graft-PCL.sup.b 32.1 2.2 312.2 27.5 81.6 18.8 84.3 0.6 .sup.acopolymer prepared via transesterification reaction .sup.bcopolymer prepared via ring opening polymerization .sup.cmaximum stress .sup.delongation at break .sup.ewater contact angle
Mechanical properties like maximum stress, elongation at break and Izod impact strength have been determined as follows.

(52) Tensile tests were performed to determine maximum stress and elongation at break with a Zwick type Z020 tensile tester equipped with a 20 kN load cell. The tests were performed on injection molded samples having the dimensions of 75 mm4 mm2 mm. A grip-to-grip separation of 50 mm was used. The samples were pre-stressed to 3 N, then loaded with a constant cross-head speed 50 mm/min. The analysis was performed to determine .sub.max and .sub.at break.

(53) Izod impact strength was measured using a Zwick/Roell HIT5.5P tester according to ISO 180-2001. The dimensions of the injection molded sample bars without notch were 60 mm10 mm4 mm. For each sample the average value reported was derived for at least five specimens. The testing was carried out at room temperature (25 C.).

(54) Surface properties were determined by water contact angle measurements. The water contact angles were measured by putting sessile drops of the liquid on the samples and monitoring the drop shape, using by contact angle goniometer DataPhysics OCA 20 Instrument at a temperature of 23 C. Sessile drops (1 l) of a distilled water were used for the advancing contact angle measurements. The ellipse method was used for extraction of the drop profile.

(55) SEM analysis of the freeze fractured samples were again performed to determine morphology using HITACHI SU8010 apparatus equipped with cold cathode field-emission source. The samples were sputter coated using Cressington Sputter Coater 108Auto with Au.

(56) Based on the SEM pictures and analysis, one can see again that the compatibilisers according to the invention improve adhesion between the two different compatibilised phases.

(57) TABLE-US-00006 TABLE 6 Materials used for the blends. M.sub.n M.sub.w [kg .Math. [kg .Math. MFR Density Materials mol.sup.1] mol.sup.1] PDI [g/10 min] [g/cm.sup.3] PP500P 61.6 410.3 6.7 3.1 0.905 (230 C./2.16 kg) PP531P 48.6 222.3 4.6 0.5 0.905 (230 C./2.16 kg) PC105 11.9 29.9 2.5 7.0 1.19 (300 C./1.2 kg) PC175 9.6 22.2 2.3 62.0 1.2 (300 C./1.2 kg) PC115 8.1 18.2 2.2 15.0 1.2 (300 C./1.2 kg) HDPE 22.0 81.9 3.7 1.8 0.952 CC253 (190 C./2.16 kg) LDPE2501 17.0 62.1 3.6 0.75 0.925 (190 C./2.16 kg) LDPE2801 19.5 77.0 3.9 0.55 0.928 (190 C./2.16 kg)

(58) The above listed SABIC materials (Table 6) were used for the preparation of the blends listed in Table 4 and Table 5. SABIC PP500P and PP531P are thereby commercial polypropylene homopolymers. HDPE CC253, LDPE2501 and LDPE2801 from SABIC are respectively high and low density polyethylenes. On the other hand, LEXAN Resin 105 from SABIC (PC105 in the Table above) and WONDERLITE-PC175 from Chi Mei Corporation (PC175 in the Table above) and WONDERLITE-PC115 from Chi Mei Corporation (PC115 in the Table above) are polycarbonates than can be produced via the phosgene route.