Patent Application
20240400791
The present invention is directed to a polypropylene composition obtainable by blending a propylene polymer with a combination of a dicarboxylic acid and a calcium salt of a fully saturated fatty acid, as well as to a process for producing the polypropylene composition, an article comprising the polypropylene composition, and a use of the combination of the dicarboxylic acid and the calcium salt of a fully saturated fatty acid for improving the impact strength of polypropylene compositions.
When cooling from a melt, polypropylene typically crystalizes into the monoclinic α-crystalline form. In addition to this α-form, polypropylene may also crystalize in the hexagonal β-crystalline form and the orthorhombic γ-crystalline form. The metastable β-form is typically characterised by improved impact strength and crack growth retention, which is advantageous for a number of applications, such as in pipes and fittings, but also in profiles and ducts, automotive parts and other technical articles.
Typically, β-crystallisation is achieved through the addition of specific β-nucleating agents, such quinacridone pigments (e.g. in EP 0 177 961 A2), amide compounds (e.g. NJstar NU-100, N,N′-dicyclohexyl-2,6-naphthalene dicarboxamide) and, more recently, heteronuclear rare earth complexes such as WBG (as originally disclosed in Xiao W. et al, J. Appl. Polym. Sci., 111, 1076-1085 (2009)).
It is also known that calcium salts of certain simply dibasic acids (such as pimelic acid and suberic acid, as in WO 2008/074494 A1) can perform well as β-nucleating agents, though these salts can be very sensitive to traces of water and other difficult to control parameters.
Whilst a number of β-nucleating agents are known in the art, they are somewhat unreliable when used in industrial processes. Quinacridone pigments furthermore introduce colour to polymer compositions, which is often not desired, depending on the end use of the composition.
As such, further β-nucleating agents having high efficiency, reliability and avoiding pigmentation are desired in the field of polypropylene development.
The present invention is based on the observation that the β-nucleation behaviour of certain dicarboxylic acids can be greatly enhanced through a synergistic interaction with calcium salts of fully saturated fatty acids.
In a first aspect, the present invention is thus directed to a polypropylene composition (PC) obtainable by blending:
In another aspect, the present invention is directed to a process for producing the polypropylene composition (PC) according to the invention, comprising the steps of:
In a further aspect, the present invention is also directed to an article, being either an extruded or a moulded article, comprising at least 90 wt.-%, more preferably at least 95 wt.-%, most preferably at least 98 wt.-% of the polypropylene composition (PC) according to the invention.
In a final aspect, the present invention is directed to a use of a dicarboxylic acid according to formula (I) (CHA) and a calcium salt of a fully saturated fatty acid (CaFA) for improving the Charpy notched impact strength of a polypropylene composition obtained by blending a propylene polymer with 0.10 to 1.00 wt.-% of the dicarboxylic acid according to formula (I) (CHA) and 0.10 to 1.00 wt.-% of the calcium salt of a fully saturated fatty acid (CaFA), wherein the Charpy notched impact strength of the polypropylene composition is in the range from 250 to 2000%, more preferably by 400 to 1500%, most preferably from 500 to 1000% higher than the Charpy notched impact strength of an equivalent polypropylene composition without either of the dicarboxylic acid according to formula (I) (CHA) or the calcium salt of a fully saturated fatty acid (CaFA), wherein the Charpy notched impact strength is determined at +23° C. according to ISO 179/leA using 80×10×4 mm3 test bars injection moulded in line with ISO 19069-2.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although, any methods and materials similar or equivalent to those described herein can be used in practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.
Unless clearly indicated otherwise, use of the terms “a,” “an,” and the like refers to one or more.
According to the present invention, the expression “propylene homopolymer” relates to a polypropylene that consists substantially, i.e. of at least 99.5 mol-%, more preferably of at least 99.8 mol-%, like of at least 99.9 mol-%, of propylene units. In another embodiment, only propylene units are detectable, i.e. only propylene has been polymerized.
A propylene random copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C12 alpha-olefins, in which the comonomer units are distributed randomly over the polymeric chain. The propylene random copolymer can comprise comonomer units from one or more comonomers different in their amounts of carbon atoms. In the following amounts are given in mol-% unless it is stated otherwise. A propylene random copolymer must contain at least 50 mol-% propylene units.
Typical for propylene homopolymers and propylene random copolymers is the presence of only one glass transition temperature.
Fully saturated fatty acids, i.e. fatty acids without any carbon-carbon double bonds, are aliphatic monocarboxylic acids with a carbon chain length of 8 to 26, more preferably 10 to 22. Specifically preferred fully saturated fatty acids are lauric acid (C12), myristic acid (C14), palmitic acid (C16) and stearic acid (C18).
The present invention is directed to a polypropylene composition (PC) obtainable by blending:
Whilst, in the broadest sense, the polypropylene composition (PC) is obtainable by blending the propylene polymer (PP), the dicarboxylic acid according to formula (I) (CHA), and the calcium salt of a fully saturated fatty acid (CaFA), it is preferred that the polypropylene composition is obtained by blending the propylene polymer (PP), the dicarboxylic acid according to formula (I) (CHA), and the calcium salt of a fully saturated fatty acid (CaFA).
One essential component is the propylene polymer (PP).
The propylene polymer (PP) may be a propylene homopolymer (h-PP) or a propylene random copolymer (r-PP), preferably a propylene homopolymer (h-PP). It is believed that the combination of the inventive beta nucleation system (i.e. CHA plus CaFA) with propylene homopolymers give especially beneficial improvements in Charpy notched impact strength.
If the propylene polymer is a random copolymer (r-PP), the comonomer content is preferably in the range from 0.01 to 10.0 mol-%, more preferably 0.05 to 5.0 mol-%, most preferably in the range from 0.10 to 3.0 mol-%.
The comonomer of the propylene random copolymer (r-PP) is preferably selected from ethylene and C4 to C8 alpha olefins, more preferably is ethylene or 1-butene (C4).
If the propylene polymer (PP) is a propylene homopolymer (h-PP), it is preferred that the propylene homopolymer (h-PP) has an isotactic pentad regularity <mmmm> determined by 13C-NMR spectroscopy in the range of 90.0 to 99.9%, more preferably in the range from 91.0 to 99.5%, most preferably in the range from 92.5 to 98.5%.
It is further preferred that the propylene polymer (PP) has a melt flow rate (MFR2), determined according to ISO 1133 at 230° C. at a load of 2.16 kg, in the range from 0.1 to 5.0 g/10 min, more preferably in the range from 0.1 to 2.0 g/10 min, most preferably in the range from 0.1 to 1.0 g/10 min.
Another essential component is the dicarboxylic acid according to formula (I) (CHA):
R1 to R4 are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, cycloalkyl, cycloalkenyl, aryl, substituted aryl, and halide and combinations thereof and optionally any adjacent R1 to R4 are linked together to form a 5-membered or 6-membered ring.
R1 to R4 are preferably independently selected from the group consisting of hydrogen and C1 to C4 alkyl, more preferably from hydrogen, methyl and ethyl.
It is particularly preferred that each of R1 to R4 are hydrogen, i.e. that the dicarboxylic acid is 4-cyclohexene-1,2-dicarboxylic acid, with the most preferred dicarboxylic acid being cis-4-cyclohexene-1,2-dicarboxylic acid.
The final essential component is the calcium salt of a fully saturated fatty acid.
Whilst the calcium salt of a fully saturated fatty acid (CaFA) may be a calcium salt of any fully saturated fatty acid, it is preferred that it is the calcium salt of a fully saturated C14 to C22 fatty acid, more preferably the calcium salt of a C16 to C20 fully saturated fatty acid, most preferably is calcium stearate.
The polypropylene composition (PC) is preferably obtainable by blending:
In one embodiment, the polypropylene composition (PC) is obtainable by blending:
In further preferred embodiment, the polypropylene composition (PC) is obtainable by blending:
It is preferred that the weight ratio of the calcium salt of a fully saturated fatty acid (CaFA) to the dicarboxylic acid according to formula (I) (CHA), [CaFA]/[CHA], is in the range from 0.90 to 2.00, more preferably in the range from 1.00 to 1.70, most preferably in the range from 1.05 to 1.40.
The polypropylene composition (PC) preferably has a melt flow rate (MFR2), determined according to ISO 1133 at 230° C. at a load of 2.16 kg, in the range from 0.1 to 5.0 g/10 min, more preferably in the range from 0.1 to 2.0 g/10 min, most preferably in the range from 0.1 to 1.0 g/10 min.
The polypropylene composition (PC) preferably has a crystallisation temperature (Tc), determined by DSC analysis, in the range from 115.0 to 130.0° C., more preferably in the range from 116.0 to 128.0° C., most preferably in the range from 118.0 to 126.0° C.
The polypropylene composition (PC) preferably has a flexural modulus, determined according to ISO 178 using 80×10×4 mm3 test bars injection moulded in line with ISO 19069-2, in the range from 1000 to 1500 MPa, more preferably in the range from 1100 to 1450 MPa, most preferably in the range from 1200 to 1400 MPa.
The polypropylene composition (PC) preferably has a Charpy notched impact strength (NIS), determined at +23° C. according to ISO 179/leA using 80×10×4 mm3 test bars injection moulded in line with ISO 19069-2, in the range from 25.0 to 100.0 KJ/m2, more preferably in the range from 30.0 to 90.0 KJ/m2, most preferably in the range from 35.0 to 85.0 KJ/m2.
It is particularly preferred that the polypropylene composition (PC) according to any one of the preceding claims, having a first melting temperature (Tm1) in the range from 157 to 167° C. and a second melting temperature (Tm2) in the range from 142 to 155° C., wherein the ratio between the enthalpy of fusion associated with the first melting temperature (ΔHm1) and the enthalpy of fusion associated with the second melting temperature (ΔHm2), ([ΔHm1]/[ΔHm2]) is in the range from 0.05 to 1.00, more preferably in the range from 0.05 to 0.80, most preferably in the range from 0.1 to 0.65,
wherein the first melting temperature (Tm1), the second melting temperature (Tm2), the enthalpy of fusion associated with the first melting temperature (ΔHm1) and the enthalpy of fusion associated with the second melting temperature (ΔHm2) are determined according to DSC analysis.
It is further preferred that the first melting temperature (Tm1) is in the range from 160 to 167° C., more preferably in the range from 163 to 166° C.
It is also further preferred that the second melting temperature (Tm2) is in the range from 145 to 153° C., more preferably in the range from 148 to 152° C.
In a further aspect, the present invention is directed to an article comprising the polypropylene composition according to the invention.
The article is either an extruded article or a moulded article. Preferably, the article is selected from the group consisting of pipes and fittings, profiles and ducts, automotive parts and technical articles.
The article comprises at least 90 wt.-%, more preferably at least 95 wt.-%, most preferably at least 98 wt.-% of the polypropylene composition (PC) as described above.
It is further preferred that the extruded or moulded article has a core beta-phase content (Kβ), determined by wide angle x-ray scattering (WAXS), in the range from 50 to 99%, more preferably in the range from 55 to 95%, most preferably in the range from 60 to 90%.
Preferably, the extruded or moulded article has a core crystallinity index (Xc) in the range from 50 to 80%, more preferably in the range from 55 to 70%, most preferably in the range from 60 to 65%.
All preferable embodiments and fallback positions for the polypropylene composition (PC) described above apply mutatis mutandis to the polypropylene composition (PC) of the article.
In another aspect, the present invention is directed to a process for producing the polypropylene composition (PC) of the invention.
Said process comprises the steps of:
In particular, it is preferred to use a conventional compounding or blending apparatus, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin-screw extruder. More preferably, mixing is accomplished in a co-rotating twin-screw extruder. The polymer materials recovered from the extruder are usually in the form of pellets.
It is particularly preferred that the polypropylene composition (PC) of the present invention is used for the production of moulded articles. It is thus preferred that the process further comprises, after step d) the step of:
Alternatively, the polypropylene composition (PC) of the present invention is used for the production of extruded articles. In such embodiments, step d) may involve:
All preferable embodiments and fallback positions for the polypropylene composition (PC) and/or the article described above apply mutatis mutandis to the process for producing the polypropylene composition (PC) and/or the article.
In a final aspect, the present invention is directed to a use of a dicarboxylic acid according to formula (I) (CHA) and a calcium salt of a fully saturated fatty acid (CaFA) for improving the Charpy notched impact strength of a polypropylene composition obtained by blending a propylene polymer with 0.10 to 1.00 wt.-% of the dicarboxylic acid according to formula (I) (CHA) and 0.10 to 1.00 wt.-% of the calcium salt of a fully saturated fatty acid (CaFA).
The improvement of the Charpy notched impact strength is achieved when the Charpy notched impact strength of the polypropylene composition is in the range from 250 to 2000%, more preferably by 400 to 1500%, most preferably from 500 to 1000% higher than the Charpy notched impact strength of an equivalent polypropylene composition without either of the dicarboxylic acid according to formula (I) (CHA) or the calcium salt of a fully saturated fatty acid (CaFA), wherein the Charpy notched impact strength is determined at +23° C. according to ISO 179/leA using 80×10×4 mm3 test bars injection moulded in line with ISO 19069-2.
In a preferred embodiment, the polypropylene composition of the use described above is the polypropylene composition (PC) as described above.
All preferable embodiments and fallback positions for the polypropylene composition (PC) described above apply mutatis mutandis to the polypropylene composition (PC) of this embodiment.
The following definitions of terms and determination methods apply for the above general description of the invention including the claims as well as to the below examples unless otherwise defined.
Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regio-regularity of the propylene homopolymers.
Quantitative 13C{1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics.
For propylene homopolymers approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transients were acquired per spectra.
Quantitative 13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.
For propylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.
Characteristic signals corresponding to regio defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253: Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950) or comonomer were observed.
The tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443: Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251).
Specifically the influence of regio-defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio-defect and comonomer integrals from the specific integral regions of the stereo sequences.
The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:
[mmmm] %=100*(mmmm/sum of all pentads)
The presence of 2,1 erythro regio-defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of regio-defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).
The amount of 2,1 erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:
P
21e=(Ie6+Ie8)/2
The amount of 1,2 primary inserted propylene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:
P
12
=I
CH3
+P
12e
The total amount of propylene was quantified as the sum of primary inserted propylene and all other present regio-defects:
P
total
=P
12
+P
21e
The mole percent of 2,1 erythro regio-defects was quantified with respect to all propylene:
[21e] mol-%=100*(P21e/Ptotal)
MFR2 (230° C.) was measured according to ISO 1133 (230° C., 2.16 kg load).
DSC analysis, melting temperature (Tm) and heat of fusion (Hf), crystallization temperature (Tc) and heat of crystallization (Hc): measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. Crystallization temperature (Tc) and heat of crystallization (Hc) are determined from the cooling step, while melting temperature (Tm) and heat of fusion (Hf) are determined from the second heating step.
The Flexural Modulus was determined according to ISO 178 method A (3-point bending test) on 80×10×4 mm3 specimens. Following the standard, a test speed of 2 mm/min and a span length of 16 times the thickness was used. The testing temperature was 23±2° C. Injection moulding was carried out according to ISO 19069-2 using a melt temperature of 230° C. for all materials irrespective of material melt flow rate.
The Charpy notched impact strength (NIS) was measured according to ISO 179 leA at +23° C. or −20° C., using injection moulded bar test specimens of 80×10×4 mm3 specimens. Injection moulding was carried out according to ISO 19069-2 using a melt temperature of 230° C. for all materials irrespective of material melt flow rate.
The measurement of wide-angle X-ray scattering (WAXS) of the samples was conducted by a Bruker D8 Discover apparatus. The diffractometer was equipped with an X-ray tube with a copper target operating at 30 kV and 20 mA and a GADDS 2-D detector. A point collimation (0.5 mm) was used to direct the beam onto the surface. The measurement was done in reflection geometry, and 28 angle in the range from 10° to 32.5° were measured. Data were collected for 300 s. Intensity vs. 2-theta curve was acquired with the same measurement parameters on an amorphous polypropylene sample, which was prepared by solvent extraction. An amorphous halo was obtained by smoothing the curve. The amorphous halo has been subtracted from the measured intensity vs. 2-theta curve to result in the crystalline curve.
The crystallinity index Xc can be defined by the area under the crystalline curve and the original spectrum using Challa, Hermans and Weidinger method [Challa F, Hermans P H, Weidinger A, Makromol. Chem. 56, 169 (1962)] as:
The amount of β-form of the polypropylene within the crystalline phase Kβ was calculated using Jones method [Turner-Jones A, Aizlewood J M, Beckett D R, Makromol. Chem. 75, 134 (1974)] according to the following equation:
where, Iβ(300) is the intensity of β(300) peak, Iα (1 10) is the intensity of α(1 10) peak, Iα (040) is the intensity of α(040) peak and Iα (130) is the intensity of α(130) peak obtained after subtracting the amorphous halo.
The amount of γ-form of isotactic polypropylene (iPP) within the crystalline phase Kγ was calculated using the method developed by Pae [Pae K D, J. Polym. Sci., Part A, 6, 657 (1968)] as:
where, Iα (130) is the intensity of α(130) peak and Iγ (117) is the intensity of γ(117) peak obtained after subtracting a base line joining the base of these peaks.
Quantification of three-phase crystalline system has been carried out following the procedure explained in Obadal M, Cermak R, Stoklasa K, Macromol. Rapid Commun. 26, 1253 (2005). For three-phase crystalline systems the following equations have been used to determine Kα (amount of α-phase), Kβ (amount of β-phase) and Kγ (amount of γ-phase);
Measurements were performed on the skin section (i.e. the outer 100 μm) and the core section (i.e. the central part) of 80×10×4 mm3 specimens as injection molded for the mechanical tests.
The inventive and comparative examples were compounded in a TSE16 twin screw extruder with a melt temperature of 210° C. and a throughput rate of 1.5 kg/h, according to the recipes given in Table 1:
h-PP1 a propylene homopolymer having an MFR2 of 0.7 g/10 min and an isotactic pentad concentration of 93.1%, commercially available from Borealis AG under the trade name HA001-A.
h-PP2 a propylene homopolymer having an MFR2 of 0.3 g/10 min and an isotactic pentad concentration of 95.2%, commercially available from Borealis AG under the trade name B-Powder-10.
AO Irganox B215, a synergistic 2:1 blend of antioxidants Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphite, CAS No: 31570-04-4) and Irganox 1010 (pentaerythritol tetrakis [3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], CAS No: 6683-19-8), available from BASF SE.
SHT synthetic hydrotalcite, available from Kisuma Chemicals under the trade name DHT-4A.
CHA cis-4-cyclohexene-1,2-dicarboxylic acid (CAS No: 2305-26-2), commercially available from SigmaAldrich.
CaSt calcium stearate (CAS No: 1592-23-0), commercially available from Bärlocher GmbH under the trade name CEASIT-1.
WBG a heteronuclear dimetal complex of lanthanum and calcium, commercially available from Guangdong Winner Functional Materials Co., China, under the trade name WBG.
As can be seen from Table 2, the combination of calcium stearate and the CHA act synergistically to affect β-nucleation in IE1. The use of CHA alone has very little effect, as demonstrated by CE2, with no melting temperature associated with the beta phase observed by DSC analysis, and an improvement of the Charpy notched impact strength of just 3% (relative to CE1), compared to the 742% improvement observed for IE1 (again relative to CE1).
This 742% improvement is notable, especially when compared to the effects observed when using other well known β-nucleating agents, such as WBG. By comparing CE3 to CE4, we can see that incorporation of WBG in CE3 leads to a Charpy NIS improvement of 240% (relative to CE4). Whilst this is a significant improvement, the performance of the inventive combination of CHA and calcium fully saturated fatty acid salt is clearly superior.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21203993.7 | Oct 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/078807 | 10/17/2022 | WO |
