Polyolefin composition obtained from recycled polyolefin

Abstract

A recycled polyolefin composition comprising: A) from 40% to 65% by weight of a recycled polypropylene composition; b) 20% to 40% by weight of a first polypropylene ethylene copolymer C) 14% to 28% by weight of the amount of a second polypropylene ethylene copolymer (A), the sum of the amount of (B) and the amount of (C) being such that the total weight of (A), (B) and (C) is 100.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a polypropylene composition comprising a recycled elastomeric material useful for the preparation of blow molded articles. BACKGROUND

[0002] Polyolefins, in particular polypropylene, are increasingly consumed in large amounts in many applications, including packaging of food and other goods, fibers, automotive parts and a wide variety of finished goods. However, said large use of polyolefins raises concerns about the environmental impact of the waste produced after the first use.

[0003] In fact, a large amount of waste plastic material currently comes from the different recycling of municipal plastic waste, mainly consisting of flexible packaging (cast film, blown film and BOPP film), rigid packaging, blow molded bottles and injection molded containers. Typically, two main polyolefin fractions are obtained, i.e. polyethylene (in particular HDPE, LDPE, LLDPE) and polypropylene (homopolymer, random copolymer, heterophasic copolymer), through steps of separation from other polymers such as PVC, PET or PS.

[0004] However, the multi-component nature of recycled materials typically leads to low mechanical and optical properties of polyolefin formulations, where part of the virgin polymer is replaced by recycled polymers.

[0005] In an effort to mitigate the deterioration of mechanical properties, the use of compatibilizing agent ingredients has been proposed in the art. For example, US 5,030,662 discloses the use of compatibilizers of the type that react with the polymer matrix under thermal and shear conditions by free radical or ionic mechanisms. An example of compatibilizer according to this document is an olefin copolymer with a polar monomer such as maleic anhydride or vinyl acetate.

[0006] WO 2007 / 071494 discloses the use of heterophasic polyolefin compositions having a flexural modulus equal to or lower than 600 MPa as compatibilizers for recycled polyolefin compositions.

[0007] It has now been surprisingly found that certain specific recycled material formulations, although based on a plurality of chemically different components, when mixed with virgin polymers, give rise to polyolefin compositions that both have good mechanical property features and achieve an optimal balance of impact properties with tensile modulus. SUMMARY

[0008] It is therefore an object of the present disclosure a recycled polyolefin composition comprising:

[0009] A) from 40 to 65 wt.%; preferably from 42 to 60 wt.%; more preferably from 45 to 58 wt.% of a recycled polypropylene composition;

[0010] B) 20 to 40 wt%; preferably 22 to 38 wt%; more preferably 25 to 35 wt% of a first polypropylene ethylene copolymer comprising:

[0011] (b1) 67 to 89 wt%; preferably 69 to 87 wt%; more preferably 73 to 83 wt% of a propylene homopolymer having:

[0012] - less than 4.0% by weight; preferably less than 3.0% by weight; more preferably less than 2.5% by weight of the fraction soluble in xylene at 25° C.; and

[0013] - melt flow rate (ISO 1133, 230°C / 5.0kg) in the range of 0.9 to 3.4 g / 10 min; preferably in the range of 1.1 to 3.0 g / 10 min; more preferably in the range of 1.3 to 2.7 g / 10 min;

[0014] -(b2) 11 to 33 wt%; preferably 13 to 31 wt%; more preferably 14 to 27 wt% of a propylene and ethylene copolymer having:

[0015] -according to 13 ethylene-derived units in an amount ranging from 35.0% to 65.0% by weight as measured by C-NMR; preferably from 38.0% to 62.0% by weight; more preferably from 42.0% to 58.3% by weight;

[0016] The polypropylene ethylene copolymer (B) further has the following characteristics:

[0017] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) in the range of 0.3 to 2.8 g / 10 min; preferably 0.5 to 2.5 g / 10 min; more preferably in the range of 0.8 to 2.1 g / 10 min;

[0018] - a fraction soluble in xylene at 25° C. in an amount ranging from 7.0% to 31.0% by weight; preferably from 9.0% to 29.0% by weight; more preferably from 11.0% to 27.0% by weight;

[0019] - an intrinsic viscosity of the fraction soluble in xylene at 25° C., measured in tetralin at 135° C., ranging from 1.9 dl / g to 4.5 dl / g; preferably from 2.2 dl / g to 4.1 dl / g; more preferably ranging from 2.5 dl / g to 3.7 dl / g;

[0020] In the polypropylene ethylene copolymer, the sum of b1) and b2) refers to the total weight of b1) and b2), which is 100.

[0021] C) 14 to 28 wt%; preferably 15 to 26 wt%; more preferably 16 to 24 wt% of a second polypropylene ethylene copolymer comprising:

[0022] - (c1) 21 to 43 wt%; preferably 23 to 41 wt%; more preferably 27 to 37 wt% of a propylene ethylene copolymer having:

[0023] -according to 13 ethylene-derived units in an amount ranging from 1.7% to 4.5% by weight, preferably from 2.0% to 4.3% by weight, and more preferably ranging from 2.6% to 3.7% by weight, as measured by C-NMR;

[0024] - less than 8.0% by weight; preferably less than 7.5% by weight; more preferably less than 7.0% by weight; even more preferably less than 6.5% by weight; preferably more than 0.5% by weight of the fraction soluble in xylene at 25° C., and

[0025] - melt flow rate (ISO 1133, 230°C / 5.0kg) in the range of 18.0 to 34.0 g / 10 min; preferably in the range of 20.0 to 32.5 g / 10 min; more preferably in the range of 22.0 to 30.1 g / 10 min;

[0026] - (c2) 57 to 79 wt%; preferably 59 to 77 wt%; more preferably 63 to 73 wt% of a propylene and ethylene copolymer having:

[0027] -according to 13 ethylene-derived units in an amount ranging from 18.0% to 36.0% by weight, preferably from 20.2% to 34.4% by weight, and more preferably ranging from 22.8% to 32.3% by weight, as measured by C-NMR;

[0028] The polypropylene ethylene copolymer (C) further has the following characteristics:

[0029] - a melt flow rate (ISO 1133, 230°C / 5.0 kg) in the range of 0.2 to 1.7 g / 10 min; preferably 0.3 to 1.4 g / 10 min; more preferably in the range of 0.4 to 1.2 g / 10 min;

[0030] - a fraction soluble in xylene at 25°C in an amount ranging from 52.0 wt% to 76.0 wt%; preferably from 54.0 wt% to 74.0 wt%; more preferably from 56.0 wt% to 72.0 wt%;

[0031] - an intrinsic viscosity, measured in tetrahydronaphthalene at 135°C, ranging from 2.1 dl / g to 4.7 dl / g; preferably from 2.4 dl / g to 4.3 dl / g; more preferably from 2.7 dl / g to 3.9 dl / g; and,

[0032] The sum of c1 ) and c2) in the composition refers to the total weight of c1 ) and c2), which is 100,

[0033] The sum of the amount of (A), the amount of (B) and the amount of (C) refers to the total weight of (A), (B) and (C), which is 100;

[0034] The recycled polypropylene composition (A) has:

[0035] with 13 an ethylene derived units content ranging from 2.50 wt% to 7.30 wt% measured by C-NMR;

[0036] with 13 a butene derived units content ranging from 0.05 wt% to 0.30 wt% measured by C-NMR;

[0037] with 13 a hexene derived units content ranging from 0.03 wt% to 0.23 wt% measured by C-NMR;

[0038] with 13 an octene derived units content ranging from 0.02 wt% to 0.50 wt% measured by C-NMR;

[0039] with 13 a polyethylene terephthalate content ranging from 0.05 wt% to 0.8 wt% measured by C-NMR

[0040] with 13 a propylene derived units content higher than 87.4 wt% measured by C-NMR

[0041] ranging from 0.9400 Kg / dm 3 to 0.9500 Kg / dm 3 ; preferably ranging from 0.9423 Kg / dm 3 to 0.9484 Kg / dm 3 ; more preferably ranging from 0.9448 Kg / dm 3to 0.9476 Kg / dm 3 Density, ISO 1183-1 ;

[0042] Melt flow rate (ISO 1133, 230°C / 2.16 kg) ranging from 1.2 to 20.3 g / 10 min; preferably ranging from 3.4 to 17.4 g / 10 min; more preferably ranging from 5.2 to 12.3 g / 10 min. DETAILED DESCRIPTION

[0043] Preferably, the recycled polypropylene composition (A) has:

[0044] Tensile modulus ranging from 1060 N / mm 2 to 1900 N / mm 2 ; preferably ranging from 1260 N / mm 2 to 1780 N / mm 2 ; more preferably ranging from 1350 N / mm 2 to 1760 N / mm 2 .

[0045] Preferably, the recycled polypropylene composition (A) has:

[0046] Charpy impact test at 23°C ranging from 2.2 KJ / m 2 to 9.0 KJ / m 2 ; preferably ranging from 3.1 KJ / m 2 to 8.2 KJ / m 2 ; more preferably ranging from 3.4 KJ / m 2 to 7.3 KJ / m 2 .

[0047] As used herein, the term “copolymer” refers to a polymer having two different repeating units.

[0048] The term “recycled” is used to denote a polymeric material derived from at least one cycle of processing into an article, as opposed to virgin polymer which is a polymeric material that has not undergone at least one cycle of processing into an article.

[0049] The term "consisting essentially of as used herein in connection with a polymer or a polymer composition means that other components can be present in the polymer or polymer composition in addition to those components which are mandatory, provided that the basic characteristics of the polymer or composition are not materially affected by their presence. According to the present disclosure, examples of components which do not materially affect the characteristics of the polymer or polymer composition when present in the polymer or polymer composition in conventional amounts are catalyst residues, antistatic agents, melt stabilizers, light stabilizers, antioxidants, antacids.

[0050] The features of the components forming the polypropylene composition are not overly linked to each other. This means that a certain preference level of one feature does not necessarily involve the same preference level of the remaining features of the same or different components. On the contrary, it is intended in the present disclosure that any component (A), (B) and (C) and any preferred range of the features of components (A), (B) and (C) can be combined with any preferred range of one or more of the features of the features of components (A) to (B) and with any possible additional components and their features described in the present disclosure.

[0051] Components B) and C) can be prepared by polymerizing propylene, optionally in a mixture with ethylene, in the presence of a catalyst comprising the product of a reaction between:

[0052] i) a solid catalyst component comprising Ti, Mg, CI and at least one internal electron donor compound;

[0053] ii) an aluminum alkyl compound, and

[0054] iii) an external electron donor compound; preferably, the external donor compound has the following general formula:

[0055] (R 7 ) a (R 8 ) b Si(OR 9 ) c wherein a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R 7 , R 8 and R 9 are alkyl, cycloalkyl or aryl radicals having from 1 to 18 carbon atoms, optionally containing heteroatoms.

[0056] The internal donor is preferably selected from esters of mono- or di-carboxylic organic acids, such as benzoic acid esters, malonic acid esters, phthalic acid esters and certain succinic acid esters. Examples of internal donors are described in US 4522930 A, EP 045977 A2 and international patent applications WO 00 / 63261 and WO 01 / 57099. Particularly suitable are phthalic acid esters and succinic acid esters. Alkyl phthalates are preferred, such as diisobutyl phthalate, dioctyl phthalate and diphenyl phthalate and benzyl butyl phthalate.

[0057] The particles of the solid component (i) can have a substantially spherical morphology and an average diameter of between 5 pm and 150 pm, preferably 20 pm to 100 pm and more preferably 30 pm to 90 pm. By particles having a substantially spherical morphology, it is meant that the ratio between the larger axis and the smaller axis is equal to or lower than 1.5, and preferably lower than 1.3.

[0058] The amount of Mg can range preferably from 8% to 30%, more preferably from 10% to 25% by weight.

[0059] The amount of Ti can range from 0.5% to 7% and more preferably from 0.7% to 5% by weight.

[0060] According to one method, the compound of formula Ti(OR) q-y X yof the formula MgCl2-pROH, wherein p is a number between 0.1 and 6, preferably 2 to 3.5, R is a hydrocarbon group having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing the alcohol and magnesium chloride under stirring conditions operating at the melting temperature of the adduct (100°C to 130°C). Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct, thus creating an emulsion which is rapidly quenched so that the adduct solidifies in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be directly reacted with the Ti compound or it can be previously subjected to a thermal controlled dealcoholation (80°C to 130°C) so as to obtain an adduct wherein the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4; the mixture is heated up to 80°C to 130°C and kept at this temperature for 0.5 hours to 2 hours. The treatment with TiCl4can be carried out one or more times. The electron donor compound can be added in the required proportions during the treatment with TiCl4.

[0061] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. Alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3may also be used, possibly in the form of mixtures with the above-mentioned trialkylaluminums. The Al / Ti ratio is higher than 1 and can preferably range between 50 and 2000.

[0062] Particularly preferred are silicon compounds (iii) wherein a is 1, b is 1, c is 2, R 7 and at least one of R 8 is selected from branched alkyl, cycloalkyl or aryl groups having 3 to 10 carbon atoms, optionally containing heteroatoms, and R 9is a C1-C10 alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl-tert- butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2-ethylpiperidyl)tert-butyldimethoxysilane, (2-ethylpiperidyl)tert- hexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Further preferred are silicon compounds wherein a is 0, c is 3, R 8 is a branched alkyl or cycloalkyl group optionally containing heteroatoms, and R 9 is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, tert-butytrimethoxysilane and tert-hexyltrimethoxysilane.

[0063] The amount of external electron donor compound (iii) is such that the molar ratio between the organoaluminum compound and said external electron donor compound (iii) is comprised between 0.1 and 200, preferably between 1 and 100, and more preferably between 3 and 50.

[0064] Components B) and C) can be prepared in a continuous sequential polymerization process, wherein component b1) or c1) is prepared in a first reactor and component (b2) or c2) is prepared in a second reactor in the presence of component b1) or c1) according to known techniques and in gas phase, or in liquid phase in the presence or absence of an inert diluent, or by mixed liquid-gas technology operation.

[0065] Component B) is preferably a commercial polymer grade, such as Moplen EP440G sold by Lyondellbasell.

[0066] Component C) is preferably a commercial polymer grade, such as Adflex Q100F sold by Lyondellbasell.

[0067] Component (A) can be a post-industrial resin (PIR) or a post-consumer resin (PCR).

[0068] A post-industrial resin (PIR) is a waste generated by a manufacturing process, which is recycled or reused in the same material.

[0069] A post-consumer resin (PCR) is defined as a recyclate derived from a final product that has completed its life cycle as a consumer item and would have otherwise been disposed of as waste.

[0070] If desired, the final composition comprising (A) + (B) can be chemically treated with organic peroxides in order to reduce the average molecular weight and increase the melt flow index up to the values required for the specific application.

[0071] Preferably, the tensile modulus of the whole recycled polyolefin composition ranges from 740 MPa to 1640 MPa, more preferably from 840 MPa to 1440 MPa; even more preferably from 950 MPa to 1390 MPa.

[0072] The Charpy impact value at 23 °C ranges preferably from 30.0 KJ / m 2 to 60.0 KJ / m 2 ; more preferably it ranges from 35.0 KJ / m 2 to 55.1 KJ / m 2 ; even more preferably it ranges from 40.5 KJ / m 2 to 50.6 KJ / m 2 .

[0073] The whole propylene composition of the present disclosure can be obtained by mechanically blending components (A), (B) and (C) according to conventional techniques.

[0074] The final composition comprising components (A), (B) and (C) can be added with conventional additives, fillers and pigments commonly used in olefin polymers, such as nucleating agents, extender oils, mineral fillers and other organic and inorganic pigments. In particular, the addition of inorganic fillers such as talc, calcium carbonate and mineral fillers also brings an improvement in some mechanical properties such as flexural modulus and HDT. Talc can also have a nucleating effect.

[0075] For example, the nucleating agent can be added to the composition of the present disclosure in an amount ranging from 0.05 wt% to 2 wt%, more preferably from 0.1 wt% to 1 wt% with respect to the total weight.

[0076] The propylene polymer composition of the present disclosure can be used for the production of blow molded articles such as bottles and containers.

[0077] The following examples are given by way of illustration and not by way of limitation of the present disclosure.

[0078] Examples

[0079] Characterization

[0080] Xylene soluble (XS) fraction at 25 °C

[0081] Into a glass flask equipped with a refrigerated and magnetic stirrer, 2.5 g of polymer and 250 ml of xylene were introduced. The temperature was raised to the boiling point of the solvent in 30 minutes. The resulting clear solution was then kept under reflux and stirred for 30 minutes. The closed flask was then kept in an ice-water bath for 30 minutes and then in a thermostated water bath at 25°C for 30 minutes. The resulting solid was filtered on a fast filter paper. 100 ml of filtrate were poured into a pre-weighed aluminum container which was heated on a heating plate under a nitrogen stream to remove the solvent by evaporation. The container was then kept in an oven at 80°C under vacuum until a constant weight was reached. The weight percentage of polymer soluble in xylene at room temperature was then calculated.

[0082] The content of the xylene soluble fraction was expressed as a percentage of the original 2.5 grams, then the xylene insoluble percentage (%) was expressed by difference (complementary to 100%).

[0083] Melt flow rate (MFR)

[0084] Measured according to ISO 1133-1 at 230°C with a load of 2.16 kg or 5 kg as specified.

[0085] Intrinsic viscosity (IV)

[0086] The sample was dissolved in tetralin at 135°C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) was surrounded by a cylindrical glass jacket; this setup allowed temperature control with a circulating thermostated liquid. The downward passage of the meniscus was timed by a photoelectric device.

[0087] The passage of the meniscus in front of the upper lamp started a counter with a quartz crystal oscillator. When passing the lower lamp, the meniscus stopped the counter and the efflux time was recorded: this was converted into intrinsic viscosity values by the Huggins' equation (Huggins, M.L., J. Am. Chem. Soc., 1942, 64, 2716) provided that the flow time of the pure solvent was known under the same experimental conditions (same viscometer and same temperature). A single polymer solution was used to determine [η].

[0088] Polydispersity index : determined by using a parallel plate rheometer of the type RMS-800 sold by RHEOMETRICS (USA) operating with an oscillation frequency increasing from 0.1 rad / sec to 100 rad / sec at a temperature of 200°C. According to the cross modulus, the P.I. can be derived by the following equation:

[0089] P.I. = 105 / Gc

[0090] where Gcis the cross-over modulus defined as the value at G' = G" (in Pa), where G' is the storage modulus and G" is the loss modulus.

[0091] Evaluation of13C NMR spectra of ethylene, propylene, 1-butene, 1-hexene and 1-octene copolymers

[0092] In 13 In the13C NMR spectra only signals from ethylene, propylene, 1-butene, 1-hexene and 1-octene copolymers were considered (the assignment of the peaks relevant for the quantification is reported in Table 1). From the integration of the relevant peaks in the13C NMR spectra (considering that the peak of the antioxidant AO1010 can overlap) the triad distribution was obtained (only EBE, EHE and EOE were considered because the amount of these comonomers is very low): 13

[0093] PPP = 100 I 11 / ∑

[0094] For I3 / I4< 1 : PPE = 100 I3 / ∑

[0095] For I3 / I4> 1 : PPE = 100 (I8 - 6I4) / ∑

[0096] EPE = 100 I7 / ∑

[0097] EBE = 100 I1 / ∑

[0098] EHE = 100 I6 / ∑

[0099] EOE = 100 (I2 - I6) / ∑

[0100] XEX = 100 I 13 / ∑

[0101] XEE = 100 (I 12 - I2) / ∑

[0102] EEE = 100 (0.5 (I 10 - I2) + 0.25 (I9 + I8)) / ∑

[0103] where:

[0104] ∑ = I 11 + (I3 or (I8 - 6I4)) + I7 + I1 + I6 + I2 - I6 + I 13 + I 12 - I2 + 0.5 (I 10- I2) + 0.25 (I9 + I8)

[0105] and I n ​are the areas of the corresponding carbons following the numbering scheme reported in Table 1 and X can be propylene, 1-butene, 1-hexene or 1-octene. The mole contents of ethylene, propylene, 1-butene and 1-octene are obtained from the triplets using the following relationships:

[0106] P(m%) = PPP + PPE + EPE

[0107] B(m%) = EBE

[0108] H(m%) = EHE

[0109] O(m%) = EOE

[0110] E(m%) = EEE + XEE + XEX

[0111] The mole contents are converted into weight using the monomer molecular weights.

[0112] Evaluation of the 1H NMR spectra

[0113] From 1 The mole contents of polyethylene terephthalate (PET), polystyrene (PS) and ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer were obtained from the 1H spectra.

[0114] The aromatic hydrogen peaks of PET and PS were used (allocation according to Table 2), while the amount of ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer was determined by integrating all aliphatic hydrogens (from which the contribution of 3 aliphatic hydrogens of polystyrene was subtracted).

[0115] The mole amounts of PET, PS and E / P / B / H / O copolymer were evaluated from the following relationships:

[0116] PET = 100 0.25 I a / ∑

[0117] PS = 100 0.5 I c / ∑

[0118] Total aliphatic E / P / B / H / O copolymer = 100 0.5 (I e - 3 PS - 9 I d ) / ∑

[0119] where ∑ = 0.25 I a + 0.5 I c + 0.5 (I d - 3 PS - 100 0.5 (I e - 3 PS - 9 I d ) / ∑

[0120] The molar content is converted into weight percent using the monomer molecular weights to estimate the mass contribution from the ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymer, taking into account the MW of CH2.

[0121] The weight content of P, E, B, H and O obtained from the C spectrum is rescaled to obtain the weight percent in the whole sample by multiplying each value (wt%) from the triplet by the following rescaling factor "RF": 13 The weight content of P, E, B, H and O obtained from the C spectrum is rescaled to obtain the weight percent in the whole sample by multiplying each value (wt%) from the triplet by the following rescaling factor "RF":

[0122] RF = [100 - PET (wt%) - PS (wt%)] / 100, where PET (wt%) and PS (wt%) are the weight content of PET and PS obtained from the H spectrum. 1 The composition obtained from the H spectrum.

[0123] Table a assignment of the C NMR spectrum of ethylene / propylene / 1-octene / 1-butene copolymers 13 Assignment of the C NMR spectrum

[0124] No. Chemical shift (ppm) Carbon Sequence 1 39.6 [CAT δδ ]]> EBE 2 38.8 [CAT δδ ]]> EOE + EHE 3 38.2-37.6 [SA αγ ]]> PE 4 36.2 CH2 AO 1010 6 34.0 4B4 EHE 7 33.3-33.2 [CAT δδ ]]> EPE 8 30.8–30.7 [TECHNICAL FIELD] βδ ]] PPE 8 30.3 [SA γδ ]]> XEEE 9 30.2 [SA γδ ]] PEEE 10 29.9 [SA δδ+ 4B6 EEE + O 11 28.8–28.2 [CAT ββ ]]> PPP 12 27.4–26.7 <![CDATA[S βδ +5B6]]> XE + O 13 24.7–24.1 [SA ββ ]]> XEX

[0125] Table b assignment of the C NMR spectrum of ethylene / propylene / 1-butene / 1-hexene / 1-octene copolymers containing PS and PET 1 Assignment of the H NMR spectrum

[0126]

[0127] Ethylene (C2) content

[0128] Assignment of the C NMR 13 C NMR

[0129] The C NMR spectrum was acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe, operating in Fourier transform mode at 160.91 MHz at 120 °C. 13 C NMR spectrum was acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe, operating in Fourier transform mode at 160.91 MHz at 120 °C.

[0130] S ββ The peak of the S carbon at 29.9 ppm (nomenclature according to "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Patterns" C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536) was used as internal reference. The samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 8 wt / v% concentration at 120 °C. Each spectrum was acquired with a 90° pulse, a delay of 15 seconds between pulse and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.

[0131] The assignment of the spectra, the evaluation of the triad distribution and the composition were made according to Kakugo ("Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with δ-titanium trichloride-diethylaluminum chloride" M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules 1982, 15, 4, 1150-1152) using the following equations:

[0132] PPP = 100 T ββ / S PPE = 100 T βδ / S EPE = 100 T δδ / S

[0133] PEP = 100 S ββ / S PEE = 100 S βδ / S EEE = 100 (0.25 S γδ + 0.5 S δδ ) / S

[0134] S = T ββ + T βδ + T δδ + S ββ + S βδ + 0.25 S γδ + 0.5 S δδ

[0135] The mole percentage of ethylene content was evaluated using the following equation:

[0136] The weight percentage of ethylene content was evaluated using the following equation:

[0137]

[0138] where P mol% is the mole percentage of propylene content, and MW E and MW P are the molecular weight of ethylene and propylene, respectively.

[0139] The product of the reactivity ratios r1r2 was calculated according to Carman (C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977; 10, 536) as:

[0140]

[0141] The tacticity of the propylene sequences was calculated as mm content from the ratio of the integrals of the peaks at 28.90 ppm to 29.65 ppm (PPP mmT ββ (29.80 ppm to 28.37 ppm) to the total T ββ (29.80 ppm to 28.37 ppm) to the total T

[0142] Samples for mechanical testing

[0143] The samples were obtained according to ISO 1873-2:2007.

[0144] The Charpy impact test was determined according to ISO 179-1 eA and ISO 1873-2.

[0145] Yield elongation: measured according to ISO 527.

[0146] Elongation at break: measured according to ISO 527

[0147] Stress at break: measured according to ISO 527.

[0148] Tensile modulus according to ISO 527-2.

[0149] Melting and crystallization point

[0150] The melting point was measured by using a DSC instrument according to ISO 11357-3, on a sample of weight between 5 and 7 mg, under an inert N2 flow, in cooling and heating at a scan rate of 20 °C / min. The instrument was calibrated with indium.

[0151] Density, measured according to ISO 1183-1

[0152] Examples

[0153] Example 1

[0154] Component A

[0155] Component A is a recycled polymer grade from raffia bag. The properties of the polymer are reported in Table 1.

[0156] Table 1

[0157]

[0158]

[0159] Component B)

[0160] Component B is a commercial grade Moplen EP440G sold by LyondellBasell, which can be synthesized according to procedures known in the art, Moplen EP440G having the properties listed in Table 2.

[0161] Table 2

[0162] Component b1) XS wt% 2.0 MFR 230°C / 2.16 kg g / 10 min 1.9 Separation wt% 79 Component b2) C2 content wt% 51.0 Separation wt% 21 Total composition MFR 230°C / 5 kg g / 10 min 1.3 XS wt% 19 IV on XS dl / g 3.0

[0163] Fraction of XS soluble in xylene at 25°C

[0164] C2 ethylene derived units

[0165] IV intrinsic viscosity

[0166] Component C)

[0167] Component C is a commercial grade Adflex Q100F sold by LyondellBasell, which can be synthesized according to procedures known in the art, Adflex Q100F having the properties listed in Table 3.

[0168] Table 3

[0169]

[0170]

[0171] Fraction of XS soluble in xylene at 25°C

[0172] C2 ethylene derived units

[0173] IV intrinsic viscosity

[0174] Components A), B) and C) have been blended in an extruder (Berstorff extruder). The polymer pellets were extruded in a twin-screw extruder under nitrogen atmosphere at a rotation speed of 250 rpm and a melting temperature of 200°C to 250°C. The composition is reported in Table 4 and the characterization of the obtained composition is reported in Table 5.

[0175] Table 4

[0176] Example 1 Component A wt% 50 Component B) wt% 30 Component C) wt% 20

[0177] Table 5

[0178] Unit Example 1 Melt flow rate g / 10 min 2.96 Charpy 23°C KJ / m 2 ]]> 44.9 Charpy 0°C KJ / m 2 ]]> 7.2 Tensile modulus [N / mm 2 ]]> 1050 Yield stress [N / mm 2 ]]> 22.4 Yield elongation ％ 10.5 Breaking stress [N / mm 2 ]]> 18.7 Breaking elongation ％ 597 Hc J / g -88 Hm J / g 74.4 Tm ℃ 163.8 Tc ℃ 118.1 HDT 0.45 Mpa ℃ 78.7

Claims

1. A recycled polyolefin composition, comprising: A) from 40 wt% to 65 wt% of a recycled polypropylene composition; B) from 20 wt% to 40 wt% of a first polypropylene ethylene copolymer, comprising: (b1) from 67 wt% to 89 wt% of a propylene homopolymer having: - a fraction soluble in xylene at 25 °C lower than 4.0 wt%; and - a melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranging from 0.9 to 3.4 g / 10 min; (b2) from 11 wt% to 33 wt% of a propylene and ethylene copolymer having: - according to 13 units derived from ethylene in an amount ranging from 35.0 wt% to 65.0 wt%; said polypropylene ethylene copolymer (B) further having the following characteristics: - a melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranging from 0.3 to 2.8 g / 10 min; - a fraction soluble in xylene at 25 °C in an amount ranging from 7.0 wt% to 31.0 wt%; - an intrinsic viscosity measured in tetraline at 135 °C ranging from 1.9 dl / g to 4.5 dl / g for the fraction soluble in xylene at 25 °C; the sum of b1) and b2) in said polypropylene ethylene copolymer refers to the total weight of b1) and b2) being 100, C) from 14 wt% to 28 wt% of a second polypropylene ethylene copolymer, comprising: (c1) from 21 wt% to 43 wt% of a propylene ethylene copolymer having: - according to 13 units derived from ethylene in an amount ranging from 1.7% to 4.5% by weight; - a fraction soluble in xylene at 25 °C lower than 8.0 wt%, preferably higher than 0.5 wt%, and - a melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranging from 18.0 to 34.0 g / 10 min; (c2) from 57 wt% to 79 wt% of a propylene and ethylene copolymer having: - according to 13 units derived from ethylene in an amount ranging from 18.0 wt% to 36.0 wt%; said polypropylene ethylene copolymer (c) further having the following characteristics: - - a melt flow rate (ISO 1133, 230 °C / 5.0 kg) ranging from 0.2 to 1.7 g / 10 min; - a fraction soluble in xylene at 25 °C in an amount ranging from 52.0 wt% to 76.0 wt%; - an intrinsic viscosity measured in tetraline at 135 °C ranging from 2.1 dl / g to 4.7 dl / g for the fraction soluble in xylene at 25 °C; and, the sum of c1) and c2) in said composition refers to the total weight of c1) and c2) being 100, the sum of the amount of (A), the amount of (B) and the amount of (C) refers to the total weight of (A), (B) and (C) being 100; said recycled polypropylene composition (A) having: With 13 an ethylene derived units content in the range of 2.50 wt.-% to 7.30 wt.-% as measured by C-NMR; With 13 a butene derived unit content in the range of 0.05 wt% to 0.30 wt% as measured by C-NMR; With 13 a hexene derived unit content in the range of 0.03 wt% to 0.23 wt% as measured by C-NMR; With 13 C-NMR measured octene derived unit content in the range of 0.02 wt% to 0.50 wt%; With 13 Polyethylene terephthalate content in the range of 0.05 wt% to 0.8 wt% as measured by C-NMR With 13 propylene derived units content higher than 87.4 wt% measured by C-NMR in the range of 0.9400 Kg / dm 3 to 0.9500 Kg / dm 3的密度，ISO1183-1 ; - a melt flow rate (ISO 1133, 230 °C / 2.16 kg) ranging from 1.2 to 20.3 g / 10 min.

2. The recycled polyolefin composition according to claim 1, wherein component (A) ranges from 42 wt% to 60 wt%; component (B) ranges from 22 wt% to 38 wt%; and component C) ranges from 15 wt% to 26 wt%.

3. The recycled polyolefin composition according to claim 1, wherein in component B) component b1) ranges from 69 wt% to 87 wt%; and component b2) ranges from 13 wt% to 31 wt%.

4. The recycled polyolefin composition according to claim 1, wherein in component C) component c1) ranges from 23 wt% to 41 wt%; and component c2) ranges from 59 wt% to 77 wt%.

5. The recycled polyolefin according to claim 1 claim wherein in component c1 ) the amount of said units derived from ethylene is in the range of 2.0 wt% to 4.3 wt% according to 13 The amount of said units derived from ethylene measured by C-NMR is in the range of 2.0 wt% to 4.3 wt%.

6. The recycled polyolefin composition according to claim 1, wherein component B) has a fraction soluble in xylene at 25°C in an amount ranging from 9.0 wt% to 29.0 wt%.

7. The recycled polyolefin composition according to any one of the preceding claims, wherein component (C) has a fraction soluble in xylene at 25°C in an amount ranging from 54.0 wt% to 74.0 wt%.

8. The recycled polyolefin composition according to claim 1, wherein component (B) has a fraction soluble in xylene at 25°C an intrinsic viscosity measured in tetraline at 135°C ranging from 2.2 dl / g to 4.1 dl / g.

9. The recycled polyolefin composition according to claim 1, wherein component (C) has a fraction soluble in xylene at 25°C an intrinsic viscosity measured in tetraline at 135°C ranging from 2.4 dl / g to 4.3 dl / g.

10. The recycled polyolefin composition according to claim 1, wherein in component A) the melt flow rate (ISO 1133-1, 230°C / 2.16 kg) ranges from 3.4 to 17.4 g / 10 min.

11. The recycled polyolefin composition according to claim 1, wherein in component (B) the melt flow rate (ISO 1133, 230°C / 5.0 kg) ranges from 0.5 to 2.5 g / 10 min.

12. The recycled polyolefin composition according to claim 1, wherein in component (C) the tensile modulus measured according to ISO 527-2 ranges from 1020 N / mm 2 to 1630 N / mm 2 .

13. The recycled polyolefin composition according to claim 1, wherein in component (C) the melt flow rate (ISO 1133, 230°C / 5.0 kg) ranges from 0.3 to 1.4 g / 10 min.

14. The recycled polyolefin composition according to claim 1, wherein component A) has the density, ISO 1183-1, ranging from 0.9423 Kg / dm 3 to 0.9484 Kg / dm 3 of the density, ISO 1183-1.

15. A blown article obtained from the recycled polyolefin composition according to claim 1.

Images