Glass Fiber Reinforced Polypropylene Composition

Abstract

A glass fiber-reinforced polypropylene-based composition containing a propylene-1-butene random copolymer or an ethylene-propylene random copolymer, a high-pressure polyethylene acrylate copolymer, and short glass fibers.

Description

Technical Field

[0001] The present invention relates to a glass fiber reinforced material suitable for applications having high requirements regarding tensile properties and elongation properties.

Background Art

[0002] Fiber reinforced compositions containing a metallocene-derived polypropylene random copolymer together with glass fibers and an adhesion promoter are known from European Patent Application Publication No. 3105287. However, the elongation at break (%) in a tensile test is not sufficient for applications with strict requirements. Furthermore, in the automotive industry, there has been a particular need for many years for a composition suitable for interior parts having an extremely soft touch. Today, the interior parts of top-class passenger cars are evaluated as a whole by their touch, and in this case, customers tend to require the rigidity conventionally expected for such articles, along with a touch like that of leather. Since leather-polymer composites make recycling more complicated, this object is even more important.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0004] Accordingly, the present invention is a glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO1133, 2.16 kg; 230 ° C) of 1.0 to 50 g / 10 min, a) 40 to 55% by weight of aa) a melting temperature (DSC; ISO11357-3) of 135 to 150 ° C, ab) Content of units derived from 1-butene of 3.0 to 9.0% by weight or content of units derived from ethylene of 2.0 to 6.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate MFR2 (ISO 1133, 2.16 kg; 230 °C) of 8.0 to 120 g / 10 min a propylene-1-butene or ethylene-propylene random copolymer having, b) a high-pressure polyethylene acrylate copolymer having a density of 910 to 935 kg / m 3 which may contain units derived from vinyltrimethoxysilane, c) 10 to 30% by weight of short glass fibers, d) 0.5 to 2.5% by weight of a coupling agent and all amounts are based on the total weight of the glass fiber reinforced polypropylene-based composition, there is provided a glass fiber reinforced polypropylene-based composition.

[0005] The present invention further provides an article comprising the glass fiber reinforced polypropylene-based composition.

[0006] The present invention further relates to the use of the glass fiber reinforced polypropylene-based composition for replacing a leather-polymer composite.

[0007] The melting temperature of the propylene-1-butene or ethylene-propylene random copolymer does not substantially overlap with the melting point of the high-pressure polyethylene acrylate copolymer having a density of 910 to 935 kg / m 3 which may contain units derived from vinyltrimethoxysilane, so it is obvious that it can be measured for the entire glass fiber reinforced polypropylene-based composition.

[0008] The propylene random copolymer contained in the glass fiber reinforced polypropylene composition of the present invention may be a propylene-1-butene random copolymer in the first embodiment, or an ethylene-propylene random copolymer in the second embodiment. The first embodiment, i.e., the propylene-1-butene copolymer, is preferred for better rigidity.

[0009] The glass fiber reinforced polypropylene composition described herein preferably contains 0.05 to 0.9% by weight of a slip agent based on the total weight of the glass fiber reinforced polypropylene composition. More preferably, the slip agent is a wax containing erucic acid amide.

[0010] In a further independently preferred embodiment, the high-pressure polyethylene acrylate copolymer contains units derived from butyl acrylate.

[0011] The glass fiber reinforced polypropylene composition according to the present invention more preferably contains a high-pressure polyethylene acrylate copolymer containing units derived from vinyltrimethoxysilane.

[0012] Even more preferably, the described glass fiber reinforced polypropylene composition a) 7.0 to 12.0% by weight of units derived from butyl acrylate, and / or b) 0.1 to 4.0% by weight of units derived from vinyltrimethoxysilane and contains a high-pressure polyethylene acrylate copolymer. The amount thereof 1 can be easily detected by 1H-NMR.

[0013] In another aspect, the glass fiber reinforced polypropylene composition can be obtained by blending glass fibers having a fiber length of 2 to 5 mm, i.e., the fiber length is the length before blending.

[0014] The glass fiber reinforced polypropylene-based composition described in this specification usually also contains a carbon black pigment. The carbon black pigment is mixed in the form of a masterbatch, and in this case, the base polymer described in this specification is also suitable as a carrier polymer for the carbon black.

[0015] The glass fiber reinforced polypropylene-based composition according to the present invention preferably contains a propylene-1-butene or ethylene-propylene random copolymer having a melting temperature of 141 to 148 °C.

[0016] The glass fiber reinforced polypropylene-based composition according to the present invention more preferably contains a propylene-1-butene random copolymer having a content of units derived from 1-butene of 4.0 to 6.0% by weight. In addition, it is even more preferable that the propylene-1-butene random copolymer is the only random propylene copolymer contained in the glass fiber reinforced polypropylene-based composition. Most preferably, the propylene-1-butene random copolymer having a content of units derived from 1-butene of 4.0 to 6.0% by weight has a melting temperature of 141 to 148 °C.

[0017] In a further aspect, the glass fiber reinforced polypropylene-based composition described in this specification has at least two melting points, namely a first melting point in the range of 95 to 103 °C and a second melting point in the range of 135 to 150 °C.

[0018] The glass fiber reinforced polypropylene-based composition preferably has a tensile strength of at least 50.0 MPa and an elongation at break of at least 5.0% when determined in a tensile test on an injection molded test piece.

[0019] When the glass fiber reinforced polypropylene-based composition described in this specification c) a slip agent which is an erucic acid amide-containing wax in an amount of 0.05 to 0.9% by weight based on the total weight of the glass fiber reinforced polypropylene-based composition is preferably included.

[0020] In a further aspect, the present invention relates to an article comprising the glass fiber reinforced polypropylene-based composition described herein. It is particularly preferred that the glass fiber reinforced polypropylene-based composition is present in an amount of at least 98.0% by weight based on the total weight of the article. It is also preferred that the article is an automotive interior article.

[0021] The present invention also relates to the use of the glass fiber reinforced polypropylene-based composition described herein for replacing a leather-polymer composite.

Embodiments for Carrying Out the Invention

[0022] In the following, more preferred embodiments will be discussed. The present invention preferably is a glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 1.0 to 50 g / 10 min, comprising a) 40 to 55% by weight of aa) a propylene-1-butene random copolymer having a melting temperature (DSC; ISO 11357-3) of 135 to 150 °C, ab) a content of units derived from 1-butene of 3.0 to 9.0% by weight (determined by NMR spectroscopy), ac) a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 8.0 to 120 g / 10 min and b) 20 to 40% by weight of a high-pressure polyethylene acrylate copolymer having a density of 910 to 935 kg / m 3 and optionally containing units derived from vinyltrimethoxysilane, c) 10 to 30% by weight of short glass fibers, d) 0.5 to 2.5% by weight of a coupling agent, e) 0.05 to 0.9% by weight of a slip agent wherein all amounts are based on the total weight of the glass fiber reinforced polypropylene-based composition.

[0023] The present invention preferably relates to a glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 1.0 to 50 g / 10 min, a) 40 to 55% by weight of aa) a melting temperature (DSC; ISO 11357-3) of 141 to 148 °C, ab) a content of units derived from 1-butene of 4.0 to 6.0% by weight (determined by NMR spectroscopy), ac) a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 8.0 to 120 g / 10 min and having a propylene-1-butene random copolymer, b) 20 to 40% by weight of a high-pressure polyethylene acrylate copolymer having a density of 910 to 935 kg / m 3 and optionally containing units derived from vinyltrimethoxysilane, c) 10 to 30% by weight of short glass fibers, d) 0.5 to 2.5% by weight of a coupling agent, e) 0.05 to 0.9% by weight of a slip agent and all amounts are based on the total weight of the glass fiber reinforced polypropylene-based composition, and relates to a glass fiber reinforced polypropylene-based composition.

[0024] In yet another particularly preferred embodiment, the present invention is a glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 1.0 to 50 g / 10 min, a) 40 to 55% by weight of aa) a melting temperature (DSC; ISO 11357-3) of 141 to 148 °C, ab) a content of units derived from 1-butene of 4.0 to 6.0% by weight (determined by NMR spectroscopy), ac) a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 8.0 to 120 g / 10 min and having a propylene-1-butene random copolymer, b) a high-pressure polyethylene acrylate copolymer having a density of 910-935 kg / m³ and containing 20-40% by weight of units derived from vinyltrimethoxysilane, 3 and, c) 10-30% by weight of short glass fibers, d) 0.5-2.5% by weight of a coupling agent, e) 0.05-0.9% by weight of a slip agent, wherein all amounts are based on the total weight of the glass fiber reinforced polypropylene-based composition, relates to a glass fiber reinforced polypropylene-based composition.

[0025] For this embodiment, the high-pressure polyethylene acrylate copolymer preferably contains units derived from 7.0-12.0% by weight of butyl acrylate, and / or units derived from 0.1-4.0% by weight of vinyltrimethoxysilane.

[0026] Unless otherwise mentioned, the above particularly preferred embodiments can be combined with further aspects from this specification.

[0027] Short glass fibers (GF) The short glass fibers used in the present invention have an average (D50) fiber length (before compounding) of 1-10 mm, preferably 2-5 mm. The aspect ratio is preferably 200-400, more preferably 250-350.

[0028] Coupling agent Coupling agents for glass fiber reinforced polyolefins are known in the art and are commercially available. These resins are usually reactively modified, for example grafted polypropylenes, such as polypropylene grafted with maleic anhydride (PP-g-MAH), produced by reactive extrusion. Suitable products include Scona TPPP 8112 and Scona TPPP 9112 from Byk-Kometra in Germany. ​

[0029] Process and catalyst for propylene-1-butene or ethylene-propylene random copolymers (base polymers) For the preparation of propylene-1-butene or ethylene-propylene random copolymers, a specific catalyst system should be used. Such a catalyst system can be obtained by the metallocene catalyst complex and cocatalyst described below.

[0030] Preferred complexes of the metallocene catalyst include rac-dimethylsilanediylbis[2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4’-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4’-tert-butylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4’-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3’,5’-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4’-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-dimethyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride include the following.

[0031] Particularly preferred is rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert-butylindene-1-yl]zirconium dichloride.

[0032] Cocatalyst In order to form an active catalyst species, it is necessary to use a cocatalyst as is well known in the art. According to the present invention, a cocatalyst system comprising a boron-containing cocatalyst and an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0033] The aluminoxane cocatalyst can be of formula (I). [Chemical formula] In the formula, n is 6 to 20, and R has the following meanings.

[0034] Aluminoxane is formed by the partial hydrolysis of organoaluminum compounds such as organoaluminum compounds of the formulas AlR3, AlR2Y and Al2R3Y3, where R is, for example, C1-C10-alkyl, preferably C1-C5-alkyl or C3-C10-cycloalkyl, C7-C12-arylalkyl or C7-C12-alkylaryl and / or may be phenyl or naphthyl, and Y may be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxane is generally not a pure compound but a mixture of oligomers of formula (I).

[0035] Preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used as cocatalysts according to the present invention are not pure compounds due to their mode of preparation, hereinafter, the molar concentration of the aluminoxane solution is based on their aluminum content. Also, boron-containing cocatalysts are used in combination with aluminoxane cocatalysts.

[0036] The catalyst complex preferably includes a cocatalyst, and specific boron-containing cocatalysts are preferred. Therefore, a particularly preferred borate (boron art complex) used in the present invention contains trityl, i.e., triphenylcarbenium, ions. Accordingly, the use of Ph3CB(PhF5)4 and its analogs is particularly advantageous.

[0037] The catalyst system of the present invention is used in a supported form. The particulate carrier material used is silica or a mixed oxide such as silica-alumina, especially silica. The use of a silica support is preferred. Those skilled in the art know the procedures necessary for supporting metallocene catalysts. In a preferred embodiment, the catalyst system corresponds to ICS3 of WO 2020 / 239602 A1 pamphlet.

[0038] The propylene-1-butene or ethylene-propylene random copolymer according to the present invention is produced by a multi-step process. It is highly recommended to use a combination of a loop reactor(s) and a gas-phase reactor(s). Usually, the first reactor is a loop reactor. It is preferable to use a combination of loop-gas phase reactor 1-gas phase reactor 2. In a preferred embodiment, the polypropylene 1-butene copolymer is produced in the first loop and the first gas-phase reactor. It is particularly preferable to use a C4 / C3 ratio of 30 to 50 mol / kmol in the first loop reactor. It is even more particularly preferable to use a C4 / C3 ratio of 28 to 42 mol / kmol in the first gas-phase reactor.

[0039] Generally, the amount of catalyst used depends on the nature of the catalyst, the type and conditions of the reactor, and the properties desired for the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.

[0040] High-pressure polyethylene acrylate copolymer It may contain units derived from vinyltrimethoxysilane 910 - 935 kg / m 3High-pressure polyethylene acrylate copolymers having the density are commercially available. These are produced in tubular or autoclave high-pressure processes without using a catalyst, as described by Jeremic (Polyethylene, Ullmann’s Encyclopedia of Industrial Chemistry, 2014). Copolymers with acrylates such as methyl acrylate (EMA), ethyl acrylate (EEA), butyl acrylate (EBA) and methyl methacrylate (EMMA) are specifically described in Chapter 2.5 of the above overview. Suitable processes including copolymerization with vinyltrimethoxysilane are described, for example, in European Patent Application Publication No. 1923404 A1, International Publication No. 2005 / 023908 A1 pamphlet and European Patent Application Publication No. 3035344 A1. It is particularly preferred to use a lubricating oil in the compressor specified in European Patent Application Publication No. 3035344 A1. Preferred tubular reactor conditions are a pressure of 2100 to 2600 bar (bar) and a temperature of 280 to 320 °C.

[0041] Typical commercially available preferred products are Borealis OE4117, Borealis OE4110SI and Borealis OE2125 supplied by Borealis AG of Austria. The glass fiber reinforced polypropylene-based composition described in this specification preferably does not contain an ethylene-vinyl acetate (EVA)-based copolymer.

[0042] Additives Typical additives are acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, scratch preventers, dispersants, processing aids, lubricants, pigments, etc.

[0043] Such additives are commercially available and are described, for example, in “Plastic Additives Handbook” by Hans Zweifel, 6th Edition, 2009 (pages 1141 to 1190).

[0044] Furthermore, the term "additive (AD)" according to the present invention also includes carrier materials, particularly polymer carrier materials.

[0045] The amount of the additive is preferably in the range of 5.0% by weight or less, for example, 0.1 to 4.0% by weight, based on the glass fiber reinforced polypropylene-based composition.

Examples

[0046] Experiment Method a) MFR2 (230 °C for polypropylene polymers; 190 °C for polyethylene polymers) is measured according to ISO 1133 (230 °C, 2.16 kg load).

[0047] b) Quantification of the microstructure (positional defects) by NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the polypropylene copolymer.

[0048] Quantitative 13 C{ 1 H} NMR spectra were recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz for H and 100.62 MHz for C, respectively. All spectra were recorded using a 10 mm extended temperature probe head optimized for 125 °C 1 H and 13 C, and nitrogen gas was used for all pneumatic pressures. 13 C.

[0049] Approximately 200 mg of the material was dissolved in 1,2 - tetrachloroethane - d2 (TCE - d2). To ensure a homogeneous solution, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen mainly for the high resolution required for the quantification of the tacticity distribution (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, using the NOE and the bilinear 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) transient signals were acquired per spectrum.

[0050] Quantitative 13 C{ 1 H} NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined from the integral values using a proprietary computer program.

[0051] For propylene homopolymers, all chemical shifts are referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm as an internal standard.

[0052] Positional 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 characteristic signals corresponding to the comonomer were observed.

[0053] The presence of 2,1-erythro positional defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of positional defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

[0054] The amount of 2,1-erythro positional defects was quantified using the average integral values of the two characteristic methyl sites at 17.7 and 17.2 ppm. P 21e =(I e6 +I e8 ) / 2

[0055] The amount of 1,2-primary inserted propene was quantified based on the methyl region. At that time, corrections were made for the sites included in this region but not related to primary insertion and the primary insertion sites excluded from this region. P 12 =I CH3 +P 21e

[0056] The total amount of propene was quantified as the sum of the primary inserted propene and all other existing positional defects present. P 全 =P 12 +P 21e

[0057] The mole percent of 2,1-erythro positional defects was quantified relative to the total propene. [21e] mol% = 100×(P21e / P 全 )

[0058] c) Comonomer content of 1-butene in propylene-1-butene copolymer (P) Quantitative 13 C{ 1 H} NMR spectra were recorded in the molten state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 MHz for H and 125.76 MHz for C, respectively. All spectra were recorded at 180 °C 1 H and 13 C. 13A 7 mm magic angle spinning (MAS) probe head optimized for C was used and all measurements were recorded using nitrogen gas. Approximately 200 mg of the material was loaded into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setting was chosen mainly because of the high sensitivity required for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207: 382.; Parkinson, M., Klimke, K., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208: 2128.; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single pulse excitation using NOE (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207: 382; Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37: 813.) and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239.; Griffin, J.M., Tripon, C., Samoson, A., Filip, C., and Brown, S.P., Mag. Res. in Chem. 2007 45, S1, S198) at a short recycle delay of 3 s was employed. A total of 16384 (16k) transient signals were acquired per spectrum.

[0059] Quantitative 13 C{ 1The 1H NMR spectra were processed, integrated, and the relevant quantitative characteristics were determined from the integral values. All chemical shifts were referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm as an internal standard.

[0060] Basic comonomer content method Spectral analysis method Characteristic signals corresponding to the incorporation of 1-butene were observed, and the comonomer content was quantified as follows.

[0061] The amount of 1-butene incorporated in the isolated sequence of PPBPP was quantified using the integral value of the αB2 site at 43.6 ppm, taking into account the number of reporting sites per comonomer. B = I α / 2

[0062] The amount of 1-butene incorporated in the two consecutive sequences of PPBBPP was quantified using the integral value of the ααB2B2 site at 40.5 ppm, taking into account the number of reporting sites per comonomer. BB = 2 × I αα

[0063] When two consecutive incorporations were observed, the amount of 1-butene incorporated in the isolated sequence of PPBPP had to be corrected due to the overlap of the signals αB2 and αB2B2 at 43.9 ppm. B = (I α -2 × I αα ) / 2

[0064] The total 1-butene content was calculated based on the sum of the 1-butene incorporated isolatedly and the 1-butene incorporated continuously. B 全 = B + BB

[0065] The amount of propene was quantified based on the major Sαα methylene site at 46.7 ppm, compensating for the relative amounts of the αB2 and αB2B2 methylene units of propene that were not considered (note that B and BB count the number of butane monomers per sequence, not the number of sequences). P 全=I Sαα +B+BB / 2

[0066] Next, the total molar fraction of 1-butene in the polymer was calculated as follows. f B =(B 全 / (B 全 +P 全 )

[0067] The complete integral equation for the molar fraction of 1-butene in the polymer was as follows. f B =(((I α -2×I αα ) / 2)+(2×I αα ))I Sαα +((I α -2×I αα ) / 2)+((2×I αα ) / 2))+((I α -2×I αα ) / 2)+(2×I αα ))

[0068] This simplifies as follows. f B =(Iα / 2+Iαα) / (I Sαα +Iα+I αα )

[0069] The total comonomer incorporation of 1-butene in mole percent was calculated from the molar fraction by the usual method. B [mol%]=100×fB

[0070] The total comonomer incorporation of 1-butene in weight percent was calculated from the molar fraction by a standard method. B [wt%]=100×(f B ×56.11) / ((f B ×56.11)+((1-f B )×42.08))

[0071] d) Determination of the acrylate and VTMS contents in the high-pressure copolymer Fourier transform infrared (FTIR) spectroscopy was used to determine the contents of both butyl acrylate (BA) and vinyltrimethoxysilane (VTMS) in the high-pressure polyethylene acrylate copolymer.

[0072] For butyl acrylate (BA), FTIR was performed on compression-molded plaques of the polymer to be analyzed, and the content was calculated from the ratio between the BA peak at 3450 cm -1 and the PE peak at 2020 cm -1 . In this method, it is calibrated by 13C{1H} NMR spectroscopy in the concentration range of 6 - 27 wt% BA. Alternatively, the BA content can also be directly determined by 13C{1H} NMR spectroscopy in solution. Similar methods can be applied to vinyl acetate and other acrylates. 13 C{ 1 H}NMR spectroscopy in the concentration range of 6 - 27 wt% BA. Alternatively, the BA content can also be directly determined by 13C{1H} NMR spectroscopy in solution. Similar methods can be applied to vinyl acetate and other acrylates. 13 C{ 1 H}NMR spectroscopy in the concentration range of 6 - 27 wt% BA. Alternatively, the BA content can also be directly determined by 13C{1H} NMR spectroscopy in solution. Similar methods can be applied to vinyl acetate and other acrylates.

[0073] For vinyltrimethoxysilane (VTMS), FTIR was performed on compression-molded plaques of the polymer to be analyzed, and the content was calculated from the ratio between the Si - O peak at 1095 cm -1 and the PE peak at 2664 cm -1 . In this method, it is calibrated by 13C{1H} NMR spectroscopy. Alternatively, the content can be calculated from the elemental silicon content determined by X-ray fluorescence (XRF), taking into account Mw[Si] = 28.0855 g / mol and Mw[VTMS] = 148.23 g / mol. 13 C{ 1 H}NMR spectroscopy in the concentration range of 6 - 27 wt% BA. Alternatively, the BA content can also be directly determined by 13C{1H} NMR spectroscopy in solution. Similar methods can be applied to vinyl acetate and other acrylates.

[0074] e) Melting temperature T m and crystallization temperature T c Melting temperature T mwas determined by differential scanning calorimetry (DSC) using a TA-Instruments 2920 Dual-Cell equipped with an RSC cooling device and a data station in accordance with ISO 11357-3. Heating and cooling rates of 10 °C / min were applied in the heating / cooling / heating cycle between +23 and +210 °C. The crystallization temperature (T c ) was determined from the cooling step, and the melting temperature (T m ) and the melting enthalpy (H m ) were determined in the second heating step.

[0075] f) Tensile test The tensile modulus, tensile strength and elongation at break were measured at 23 °C in accordance with ISO 527-2 (crosshead speed: 1 mm / min for the tensile modulus and 50 mm / min for the others) using injection-molded test specimens manufactured in accordance with EN ISO 1873-2 (dog 10 bone shape, 4 mm thick) and molded at 230 °C in accordance with ISO 527-2(1B).

[0076] g) Soft touch The soft touch and leather-likeness were evaluated by three well-trained panels.

[0077] Examples Catalyst preparation: The catalysts used in Invention Examples IE1 to IE4 were prepared according to the procedure described for Catalyst E2 in WO 2013 / 007650A1 by adjusting the amounts of metallocene and MAO to achieve the Al / Zr ratios shown in Table 1. This catalyst was prepolymerized offline with propylene according to the procedure described for Catalyst E2P in WO 2013 / 007650A1. The complex used was rac-anti-Me2Si(2-Me-4-(p-iBuPh)-lnd)(2-Me-4-Ph-5-OMe-6-iBu-lnd)ZrCI2. Offline prepolymerization degree 3.3 g / g, The Al / Zr molar ratio in the catalyst is 431 mol / mol, The metallocene complex content of the catalyst prepolymerized offline is 0.696 wt%.

[0078] Preparation of a propylene-1-butene or ethylene-propylene random copolymer (base polymer) having a melting temperature (Tm) in the range of 135 to 150 °C and a content of units derived from 1-butene of 3.0 to 9.0 wt% or a content of units derived from ethylene of 2.0 to 6.0 wt% and a melt flow rate of 8 to 120 g / 10 min. The conditions are shown in the following table.

[0079]

Table 1(1)

Table 1(2)

[0080] Examples IE1 to IE4 and CE1 to CE3 were prepared by compounding in a co-rotating twin-screw extruder having a screw configuration typical for glass fiber mixing using a temperature range of 200 to 240 °C. Formulation recipe of the composition.

[0081]

Table 2

[0082]

Table 3

[0083] The above composition had the following properties / parameters shown in the following table.

[0084]

Table 4

[0085] It can be seen that Comparative Example CE3 without high-pressure polyethylene acrylate copolymer does not have a sufficiently high elongation at break. Comparative Example CE2 without a coupling agent had an even lower elongation at break. Comparative Example CE1 had a good elongation at break but a low tensile strength, while all of Invention Examples IE1 to IE4 had acceptable tensile strength values of 50.0 MPa or more and at the same time had an elongation at break of at least 5.0%. The composition containing a propylene-1-butene random copolymer surprisingly showed better rigidity.

Claims

1. 1. A glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 1.0 to 50 g / 10 min, comprising: a) 40 to 55% by weight of aa) a propylene-1-butene or ethylene-propylene random copolymer having a melting temperature (DSC; ISO 11357-3) of 135 to 150 °C, ab) a content of units derived from 1-butene of 3.0 to 9.0% by weight or a content of units derived from ethylene of 2.0 to 6.0% by weight (determined by NMR spectroscopy), ac) a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 8.0 to 120 g / 10 min and, b) A high-pressure polyethylene acrylate copolymer having a density of 910 to 935 kg / m ３ and optionally containing units derived from vinyltrimethoxysilane in an amount of 20 to 40% by weight, and ３ ​ c) 10 to 30% by weight of short glass fibers, d) 0.5 to 2.5% by weight of a coupling agent wherein all amounts are based on the total weight of the glass fiber reinforced polypropylene-based composition.

2. e) 0.05 to 0.9% by weight of a slip agent based on the total weight of the glass fiber reinforced polypropylene-based composition The glass fiber reinforced polypropylene-based composition according to claim 1, further comprising.

3. The glass fiber reinforced polypropylene-based composition according to claim 1 or claim 2, wherein the high-pressure polyethylene acrylate copolymer contains units derived from butyl acrylate.

4. The glass fiber reinforced polypropylene-based composition according to any one of claims 1 to 3, wherein the high-pressure polyethylene acrylate copolymer contains units derived from vinyltrimethoxysilane.

5. The high-pressure polyethylene acrylate copolymer is 7.0 to 12.0% by weight of units derived from butyl acrylate, and / or 0.1 to 4.0% by weight of units derived from vinyltrimethoxysilane The glass fiber reinforced polypropylene-based composition according to any one of claims 1 to 4, containing.

6. The glass fiber reinforced polypropylene-based composition according to any one of claims 1 to 5, which can be obtained by blending glass fibers having an average fiber length (D50) of 2 to 5 mm.

7. The glass fiber reinforced polypropylene-based composition according to any one of claims 1 to 6, containing a carbon black pigment.

8. The glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 7, wherein the propylene-1-butene or ethylene-propylene random copolymer has a melting temperature (DSC; ISO 11357-3) of 141 to 148 °C.

9. The glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 8, comprising 40 to 50% by weight of a propylene-1-butene random copolymer as the only random copolymer, and preferably the content of units derived from 1-butene in the propylene-1-butene random copolymer is 4.0 to 6.0% by weight.

10. The glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 9, wherein the composition has at least two melting points, a first melting point in the range of 95 to 103 °C and a second melting point in the range of 135 to 150 °C (DSC; ISO 11357-3).

11. When determined according to ISO 527-2 (crosshead speed is 1 mm / min for tensile modulus and 50 mm / min for others) using an injection molding test piece manufactured according to EN ISO 1873-2 (dog 10 bone shape, thickness 4 mm) and molded at 230 °C according to ISO 527-2, the glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 10, having a tensile strength of at least 50.0 MPa and an elongation at break of at least 5.0%.

12. e) A slip agent which is an erucic acid amide-containing wax in an amount of 0.05 to 0.9% by weight based on the total weight of the glass fiber-reinforced polypropylene-based composition The glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 11, comprising.

13. An article comprising the glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 12, and preferably, the glass fiber-reinforced polypropylene-based composition is present in an amount of at least 98.0% by weight based on the total weight of the article.

14. The article according to claim 13, which is an automotive interior article.

15. Use of the glass fiber-reinforced polypropylene-based composition according to any one of claims 1 to 12 for replacing a leather-polymer composite.

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