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POLYMER COMPOSITION

20180163035 ยท 2018-06-14

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention relates to a composition comprising polypropylene, polyethylene and a compatibiliser, wherein said compatibiliser is a block copolymer comprising a polypropylene block and a polyester block, said polyester being a non-aromatic polyester and having an average M/E ratio of at least 10, wherein M is the number of backbone carbon atoms in the polyester not including the carbonyl carbons and E is the number of ester groups in the polyester.

    Claims

    1. A composition comprising polypropylene, polyethylene and a compatibiliser, wherein said compatibiliser is a block copolymer comprising a polypropylene block and a polyester block, said polyester being a non-aromatic polyester and having an average M/E ratio of at least 10, wherein M is the number of backbone carbon atoms in the polyester not including the carbonyl carbons and E is the number of ester groups in the polyester.

    2. The composition of claim 1 wherein the compatibiliser is an AB or BAB type block copolymer with A representing polypropylene and B representing polyester, or a graft block copolymer of structure AB.sub.n having a polypropylene backbone with n polyester branches grafted thereon, n being at least 1.

    3. The composition of claim 1 wherein the number of backbone carbon atoms between two neighboring ester groups in the backbone is randomly distributed over the polyester.

    4. The composition of claim 1 wherein the polyester has an average MIE ratio of at least 20.

    5. The composition of claim 1 wherein the amount of polypropylene is from 5-95 wt. % on the basis of the total amount of polyethylene and polypropylene.

    6. The composition of claim 1 wherein the amount of compatibiliser is from 0.5-10 wt. % on the basis of the sum of the amount of polypropylene and polyethylene.

    7. The composition of any claim 1 wherein said polypropylene is one or more of: a propylene homopolymer, a propylene-olefin random copolymer, a propylene-olefin block copolymer, a heterophasic 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 ethyleneC.sub.3-C.sub.8 -olefin copolymer.

    8. The composition of claim 1 wherein said polyethylene 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.

    9. The composition of claim 1 wherein the compatibiliser has a number average molecular weight of from 5000 to 250000 g/mol.

    10. The composition of claim 1 wherein in the compatibiliser the polyester is selected from one or more selected from the group consisting of polytetradecalactone, polypentadecalactone, polyhexadecalactone, poly(caprolactone-co-pentadecalactone), poly(-decalactone-co-pentadecalactone), poly(ethylene brassylate-co-pentadecalactone), poly[ethylene-1,19-nonadecanedioate], poly[ethylene-1,23-tricosanedioate], poly[propylene-1,19-nonadecanedioate], poly[propylene-1,23-tricosanedioate], poly[1,4-butadiyl-1,19-nonadecanedioate], poly[1,4-butadiyl-1,23-tricosanedioate], poly[1,6-hexadiyl-1,19-nonadecanedioate], poly[1,6-hexadiyl-1,23-tricosanedioate], poly[1,19-nonadecadiyl-1,19-nonadecanedioate], poly[1,19-nonadecadiyl-1,23-tricosanedioate], poly[1,23-tricosadiyl-1,19-nonadecanedioate], poly[1,23-tricosadiyl-1,23-tricosanedioate], poly[1,20-icosadiyl-1,20-icosa-nedioate], poly[1,6-hexadiyl-1,20-icosenedionate], poly[propylene-1,20-icosanedionate].

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

    12. An article comprising the composition of claim 1.

    13. The article of claim 12, said article being selected from the group consisting of automotive interior articles, automotive exterior articles, household appliances, pipes, films, sheets.

    14. (canceled)

    15. The composition of any claim 7 wherein said polypropylene comprises a propylene ethylene or a propylene C.sub.4-C.sub.8 -olefin random copolymer.

    16. A composition comprising polypropylene, polyethylene and a compatibiliser, wherein said compatibiliser is a block copolymer comprising a polypropylene block and a polyester block, said polyester being a non-aromatic polyester and having an average M/E ratio of at least 50, wherein M is the number of backbone carbon atoms in the polyester not including the carbonyl carbons and E is the number of ester groups in the polyester, and wherein the amount of polypropylene is from 5-95 wt. % and the amount of compatibiliser is from 5-10 wt. %, on the basis of the sum of the amount of polypropylene and polyethylene.

    Description

    EXAMPLE 1

    [0094] Typical Procedure for Synthesis of iPP-Block-PPDL Copolymers Via cROP.

    [0095] A glass crimp cap vial was charged with toluene (1.5 mL), PDL (1.08 g, 4.5 mmol), hydroxyl end-capped iPP (17.4 mg, 8.7 mol) and catalyst 2 (3.05 mg, 8.7 mol).

    [0096] 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. Table 1, entries iPP-PPDL1-iPP-PPDL9 specify the reaction conditions, molecular weight (M.sub.n and M.sub.w), PDI and the PDL conversion.

    EXAMPLE 2

    [0097] The same procedure was used as for example 1, with this difference that 2 was premixed with the hydroxyl end-capped iPP for 24 h at 100 C. Table 1, entries iPP-PPDL10-iPP-PDL15 specify the reaction conditions, molecular weight (M.sub.n and M.sub.w), PDI and the PDL conversion.

    EXAMPLE 3

    [0098] The same procedure was used as for example 2, with this difference that 1 was premixed with the hydroxyl end-capped iPP for 24 h at 100 C. Table 1, entries iPP-PPDL16-iPP-PDL21 specify the reaction conditions, molecular weight (M.sub.n and M.sub.w), PDI and the PDL conversion.

    EXAMPLE 4

    Typical Procedure for Synthesis of PP-Block-PPDL Via Reactive Extrusion.

    [0099] The extruder temperatures of chambers were set at 160 C., 180 C., 190 C. in the first, second and third zone, respectively. The extruder was fed with maleic anhydride functionalized iPP (Exxelor PO, 9 g, M.sub.n=30.7 kg.Math.mo.sup.1, PDI=3.4, 0.43 wt % of anhydride groups) and Irganox B225 (2500 ppm). Polymer was premixed for 5 minutes and subsequently the ethanolamine (0.072 g, 1.1 mmol) was added via syringe. The mixture was processed for 60 s and then the extruder chamber was evacuated. The OH-functionalized polypropylene (Exx-OH) was purified by dissolution in m-xylene at 120 C. and precipitation in a cold acetone. The product was dried in a vacuum oven for 24 h at 40 C.

    [0100] The previously prepared OH-functionalized PP was utilized for the preparation of PP-block-PPDL copolymers. In this step the extruder was fed with OH-functionalized polypropylene (Exx-OH) (5.1 g, M.sub.n=36.6 kg.Math.mol.sup.1, PDI=3.4) and polypentadecalactone (PPDL) (3.9 g, M.sub.n=115.1 kg.Math.mol.sup.1, PDI=2.4) at 190 C. with a screw speed set at 100 rpm. The polymers were premixed for 5 minutes. Then the tin (II) octoate catalyst 3 (0.045 g, 0.1 mmol) was added and the mixture was mixed for 2 minutes. 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 24 h at 40 C. Table 1, entries iPP-PPDL22-iPP-PPDL24 specify the reaction conditions, molecular weight (M.sub.n and M.sub.w), PDI and the PDL conversion.

    EXAMPLE 5

    [0101] Typical Procedure for Synthesis of iPP-Block-PPDL Copolymers Via Transesterification in the Solution.

    [0102] The OH-functionalized polypropylene (Exx-OH) (6.66 g, M.sub.n=36.6 kg.Math.mol.sup.1, PDI=3.4) and PPDL (3.33 g, M.sub.n=39.6 kg.Math.mol.sup.1, D=2.4) were placed in a three-necked round bottom flask equipped with a nitrogen inlet, reflux condenser and dissolved in m-xylene at 120 C. The solution was stirred using a magnetic stirrer. Then the catalyst 3 (0.05 g, 0.12 mmol) was added and the mixture was stirred for 24 h. The solution was poured into a beaker with cold acetone and stirred using magnetic stirrer for one hour and subsequently filtered. The copolymer was dried in a vacuum oven for 48 h at room temperature. Table 1, entries iPP-PPDL25-iPP-PPDL26 specify the reaction conditions, molecular weight (M.sub.n and M.sub.w), PDI and the PDL conversion.

    TABLE-US-00001 TABLE 1 Ring-opening polymerization of PDL initiated by hydroxyl- end capped iPP affording iPP-block-PPDL copolymers. time temperature M.sub.n M.sub.w conv. Entry Cat. PDL/cat/in [h] [ C.] [g/mol] [g/mol] PDI [%] iPP-PPDL1 2 250/1/1 2 100 57906 107022 1.9 49 iPP-PPDL2 2 250/1/1 5 100 35991 70338 2.0 77 iPP-PPDL3 2 500/1/1 2 100 8786 17591 2.0 18 iPP-PPDL4 2 500/1/1 5 100 63193 122632 1.9 68 iPP-PPDL5 2 250/1/1 24 100 60365 98079 1.6 95 iPP-PPDL6 2 500/1/1 24 100 82483 149488 1.8 90 iPP-PPDL7 2 1000/1/1 24 100 102906 187201 1.8 91 iPP-PPDL8 2 500/1/1.2 24 100 64643 124188 1.9 86 iPP-PPDL9 2 1000/1/1.2 24 100 2728 15206 5.6 10 iPP-PPDL10* 2 250/1/1 2 100 7301 23323 3.2 38 iPP-PPDL11* 2 500/1/1 2 100 4860 14339 3.0 39 iPP-PPDL12* 2 1000/1/1 2 100 5203 18039 3.5 22 iPP-PPDL13* 2 250/1/1 5 100 33659 64170 1.9 19 iPP-PPDL14* 2 500/1/1 5 100 38402 69637 1.8 61 iPP-PPDL15* 2 1000/1/1 5 100 54029 80752 1.8 64 iPP-PPDL16* 1 250/1/1 2 100 14321 25906 1.8 32 iPP-PPDL17* 1 500/1/1 2 100 17635 29213 1.7 28 iPP-PPDL18* 1 1000/1/1 2 100 traces of product iPP-PPDL19* 1 250/1/1 5 100 33801 65196 1.9 75 iPP-PPDL20* 1 500/1/1 5 100 27246 47404 1.7 38 iPP-PPDL21* 1 1000/1/1 5 100 traces of product Copolymers synthesized by transesterification/catalyst 3 contribution 0.5 wt % PP/PPDL time temperature M.sub.n M.sub.w Entry Cat. wt/wt [h] [ C.] [g/mol] [g/mol] iPP-PPDL22.sup.a 3 3/5 0.03(2 min) 190 35.4 168.2 4.8 iPP-PPDL23.sup.a 3 4/3 0.03(2 min) 190 31.7 167.5 5.3 iPP-PPDL24.sup.b 3 .sup.2/1.5 0.03(2 min) 190 30.5 207.3 6.8 iPP-PPDL25.sup.c 3 2/1 24 120 25.0 120.9 4.8 iPP-PPDL26.sup.a 3 2/1 5 120 29.9 219.7 7.4 For the reactions marked with * the catalyst was reacted with the initiator at 100 C. for 24 h. .sup.a= M.sub.n of PPDL used in the transesterification process is 85.5 kg/mol, .sup.b= M.sub.n of PPDL used in the transesterification process is 115.1 kg/mol, .sup.c= M.sub.n of PPDL used in the transesterification process is 39.6 kg/mol,

    EXAMPLE 6

    Typical Procedure for the Preparation of the Uncompatibilized Blends.

    [0103] Isotactic polypropylene (iPP) (PP575P, 8.0 g, M.sub.n=42.9 kg.Math.mol.sup.1, PDI=6.9, MFI=10.5 g/10 min (230 C., 2.16 kg)), low density polyethylene (LDPE) (2008TN00, 2.0 g, M.sub.n=12.2 kg.Math.mol-1, PDI=5.8, MFI=7.5 g/10 min (190 C., 2.16 kg)) were fed into the extruder chamber. The mixture was processed for 3 minutes at 190 C. with a screw rotation rate of 100 rpm. Afterwards the mixture was evacuated directly to a mini-injection molding machine to prepare samples for mechanical properties and morphology analysis. Table 2 entries 1, 2, 4, 6, 8 specify the blends preparation conditions.

    EXAMPLE 7

    Typical Procedure for the Preparation of the Blends Compatibilized by PP-Block-PPDL.

    [0104] Isotactic polypropylene (iPP) (PP575P, 8.0 g, M.sub.n=42.9 kg.Math.mol.sup.1, PDI=6.9, MFI=10.5 g/10 min (230 C., 2.16 kg)), low density polyethylene (LDPE) (2008TN00, 2.0 g, M.sub.n=12.2 kg.Math.mol.sup.1, PDI=5.8, MFI=7.5 g/10 min (190 C., 2.16 kg)) and the PP-block-PPDL (iPP-PPDL24, 0.5 g, M.sub.n=30.5 kg mol.sup.1, PDI=6.8) were fed into the extruder chamber. The mixture was processed for 3 minutes at 190 C. with a screw rotation rate of 100 rpm. Afterwards the mixture was evacuated directly to a mini-injection molding machine to prepare samples for mechanical properties and morphology analysis. Table 2 entries 3, 5, 7 specify the blends preparation conditions.

    TABLE-US-00002 TABLE 2 Composition of the uncompatibilized and compatibilized by PP-block-PPDL polymer blends. weight ratio [PP]/[LDPE]/[PP- Mixing time Entry Composition block-PPDL] [min] 1 PP/LDPE/PP-block-PPDL 100// 3 2 PP/LDPE/PP-block-PPDL 80/20/ 3 3 PP/LDPE/PP-block-PPDL 80/20/5 3 4 PP/LDPE/PP-block-PPDL 50/50/ 3 5 PP/LDPE/PP-block-PPDL 50/50/5 3 6 PP/LDPE/PP-block-PPDL 20/80/ 3 7 PP/LDPE/PP-block-PPDL 20/80/5 3 8 PP/LDPE/PP-block-PPDL /100/ 3 For the preparation of the blends PP-block-PPDL (entry iPP-PPDL24, Table 1) as the compatibilizer was used.

    [0105] FIG. 1 shows the DSC plots for these blends. It can be observed that the heat of crystallisation (enthalpy values) for compatibilised blends is lower as compared to blends that are not compatibilised. This is true for both the polypropylene phase as well as the polyethylene phase. Based on these observations the present inventors believe that the block copolymer as disclosed herein indeed has a compatibilising effect on blends of polyethylene and polypropylene.

    Examples for Graft Block Copolymers:

    [0106] Preparation of Polypropylene (iPP) Main Chain Having Hydroxyl-Functionalized Short Side Chain Branches

    [0107] The copolymerization of propylene/10-undecen-1-ol using C.sub.2-symmetric silyl-bridged zirconocene catalyst rac-Me.sub.2Si(2-Me-4-Ph-Ind).sub.2ZrCl.sub.2)/MAO has been conducted to synthesize randomly functionalized isotactic polypropylenes. Polymerization reactions were carried out in stainless steel Bchi reactors. Prior to the polymerization, the reactor was dried in vacuo at 40 C. and flushed with dinitrogen. Toluene solvent (70 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 a calculated amount of cocatalyst under dinitrogen atmosphere. The polymerization reaction was started by addition of the catalyst to reactor. The reactor was then pressurized to the desired pressure with propylene and the pressure was maintained for a predefined time (step D)). The propylene feed was stopped and the resulting mixture was quenched in acidified methanol (used as metal substituting agent, step E)), filtered and dried under reduced pressure at 60 C. for 24 h.

    [0108] All examples below relate to step F) of the process as disclosed herein, wherein polymer branches were formed using a previously prepared polypropylen main chain having a hydroxyl-functionalized short side chain branches.

    [0109] Typical procedure for synthesis of iPP-graft-PPDL copolymers: A glass crimp cap vial was charged with toluene (1.5 mL), PDL (1.1 g, 4.5 mmol), hydroxyl-functionalized iPP (4.9 mg, 8.7 mol) and catalyst 3 (3.05 mg, 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. Table 2, entry iPP-PPDL1- HDPE-PPDL3 specifies the reaction conditions, molecular weight (M.sub.n and M.sub.w), and the PDL conversion for the present example with catalyst 3 below.

    ##STR00004##

    [0110] Furthermore, the same procedure as above was used only with this difference that catalyst 4 below was used instead of 1. Table 2, entry iPP-PPDL4 specifies the reaction conditions, molecular weight (M.sub.n and M.sub.w), and the PDL conversion for the present example with catalyst 2 below.

    ##STR00005##

    TABLE-US-00003 TABLE 2 Ring-opening polymerization of PDL initiated by hydroxyl- functionalized iPP affording iPP-graft-PPDL copolymers. mon/cat./ time T M.sub.n conv. entry cat. initiator [h] [ C.] [g/mol] [%] iPP-PPDL1 3 250/1/1 24 100 42000 2.4 95 iPP-PPDL2 3 500/1/1 24 100 50800 2.2 94 iPP-PPDL3 3 1000/1/1 24 100 84800 1.9 40 iPP-PPDL4 4 100/1/1 24 100 64400 2.0 16