TWI589631B - Reinforced polypropylene composition - Google Patents

Description

Reinforced polypropylene composition Field of invention

This invention relates to a reinforced polypropylene composition comprising an elastomer and a block composite.

Background of the invention

Many different polymers and materials have been added to the polymer composition in an attempt to enhance the impact strength of the composition or to maintain impact strength while adding other properties. For example, U.S. Patent No. 5,118,753 (Hikasa et al.), which is hereby incorporated by reference in its entirety herein in its entirety herein in its entirety in the entire disclosure the disclosure the the the the the the the the A mixture of oil-enhanced olefin copolymer rubber and monoolefin plastic. The olefin plastic is a polypropylene polypropylene and a copolymer of an α-olefin having 2 or more carbon atoms. Modern Plastics Encyclopedia/89, issued October, 1988, vol. 65, No. 11, pp. 110-117, the disclosure of which is hereby incorporated by reference in its entirety in its entirety in Impact improvement. These include: elastomeric alloy TPE, engineered TPE, olefinic TPE (also known as thermoplastic olefin or TPO), polyurethane TPE, and styrene TPE.

Thermoplastic olefins (TPO) are typically derived from an elastomeric material such as a vinyl-based random copolymer, ethylene/propylene rubber (EPM), or ethylene/propylene diene monomer terpolymer (EPDM) and A blend of a more rigid material, such as a polypropylene in the same row, is made. Other materials or components may be added to the formulation depending on the application, including oils, fillers, and crosslinkers. TPO is typically characterized by stiffness (modulus) and low temperature impact, good chemical resistance, and a wide balance of operating temperatures. Because of this feature, TPO is used in many applications, including automotive instrument panels and wire and cable assemblies, rigid packaging, molded articles, instrument panels, and the like.

Polypropylene (PP) homopolymer or PP random copolymer provides the desired stiffness and clarity for many applications, but suffers from high Tg (for homopolymer PP, hpp, 0 ° C) Impact properties. The blending of the PP homopolymer with the PP copolymer and/or elastomer improves the toughness, but usually sacrifices its clarity and modulus.

It is to be understood that the elastomer or compatibilizer needs to promote or produce elastomer particles of sufficiently small size such that minimal volumetric impact properties are required without adversely affecting the modulus of the blend.

An additional improvement develops an elastomer that improves impact properties without adversely affecting its clarity or other preferred properties. Ideally, the modulus and clarity of the PP/propylene containing elastomer blend product should be comparable to those of the PP homopolymer.

Summary of invention

The present invention provides a composition comprising: polypropylene; An elastomer having a bimodal or multimodal molecular weight distribution characteristic and a selective bimodal or multimodal composition; a block composite as a compatibilizer; and a selective filler such as talc.

Brief description of the schema

Figure 1 shows the inversely folded GPC curve of Example 1.

Figure 2 shows the inversely folded GPC curve of Example 1.

Figure 3 shows the inversely folded GPC curve of Example 1.

Figure 4 shows the viscosity curve indicating the polymer.

Detailed description Polypropylene

The impact modified composition comprises a via and an elastomer group The product is blended with a toughened matrix polymer. In one embodiment, the matrix polymer is polypropylene. Any polypropylene known to those skilled in the art can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polypropylene include low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), and identical polypropylene (iPP). , propylene (sPP), etc., and combinations thereof.

The polypropylene content of the polymer blend or composition may range from about 0.5 to about 99% by weight, from about 10 to about 90% by weight, from about 20 to about 80% by weight, based on the total weight of the polymer blend. From about 30 to about 70% by weight, from about 5 to about 50% by weight, from about 50 to about 95% by weight, from about 10 to about 50% by weight, or from about 50 to about 90% by weight. In one embodiment, in a polymer blend The polypropylene content is about 50% by weight, 60% by weight, 70% by weight, or 80% by weight based on the total weight of the polymer blend.

Polypropylene is generally a homopolymer polypropylene of the same type, even if other types of polypropylene can be used (eg, aligned or random). a polypropylene impact copolymer (for example, wherein a primary copolymerization step for reacting ethylene with propylene) and a random copolymer (also modified by a reactor and usually containing 1.5 to 7% by weight of copolymerization with propylene) Ethylene), but can also be used in the TPO formulations disclosed herein. A complete discussion of various polypropylene polymers is contained in Modern Plastics Encyclopedia/89, issued Oct. 1988, vol. 65, No. 11, pp. 86-92, the entire disclosure of which is incorporated herein by reference. The molecular weight of the polypropylene used in the present invention, and hence the melt flow rate, will vary depending on the application. The melt flow rate of the polypropylene used herein is generally from about 0.1 g/10 min (g/10 min) to about 200 g/10 min, preferably from about 0.5 g/10 min to about 150 g/10 min. And especially from about 4 g/10 min to about 100 g/10 min. The propylene polymer can be a polypropylene homopolymer, or it can be a random copolymer, or even an impact copolymer (which already contains a rubber phase). Examples of such propylene polymers include -impact copolymers, Profax Ultra SG583 of LyondellBasell Polyolefins or INSPIRE 114 of Braskem; homopolymers, H110N or D221.00 of Braskem; random copolymers, 6D43 of Braskem; random propylene - ethylene plastomers and elastomers, such as, VISTAMAXX ^TM (manufactured by ExxonMobil), and VERSIFY ^TM (manufactured by the Dow Chemical Co.).

Multimodal molecular weight distribution (MMWD) elastomer

The multimodal molecular weight distribution (MMWD) elastomer comprises at least one high molecular weight (HMW) fraction and a low molecular weight fraction (LMW) and comprises ethylene in an polymerized form and an alpha-olefin comonomer. Suitable co-monomers for the manufacture of elastomers include styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or a combination thereof. Preferably, the MMWD elastomer has a two grade. Each fraction has a molecular weight distribution (MWD) of between 1.5 and 3. The HMW fraction has a Mw of more than 100 Kg/mol, preferably more than 150 Kg/mol, more preferably more than 200 Kg/mol. The Mw of the high MW fraction needs to be not less than 75 Kg/mol. The molecular weight of the HMW fraction is suitably in the range from 75 kg/mol to 600 kg/mol, from 100 kg/mol to 400 kg/mol, and from 150 kg/mol to 300 kg/mol. The low MW fraction has a molecular weight of less than 50 Kg/mol, preferably less than 25 Kg/mol, M _W . The Mw of the low MW fraction needs to be not less than 5 Kg/mol. The LMW fraction molecular weight suitably ranges from 5 kg/mol to 50 kg/mol, from 7 kg/mol to 25 kg/mol, from 10 kg/mol to 20 kg/mol. The high MW fraction is from 30% by weight to 90% by weight, preferably from 40% by weight to 80% by weight of the total elastomer, and more preferably from 50% by weight to 70% by weight. The low MW fraction is from 10 up to 70% by weight of the total elastomer, preferably from 20 up to 60% by weight, and more preferably from 30% to 50% by weight. This elastomer has a shear thinning characterized by I ₁₀ /I ₂ >8, more preferably >15. I ₁₀ /I _{2 is} preferably from 8 to 120, more preferably from 15 to 60, still more preferably from 25 to 45.

This elastomer has an overall density of <0.90 g/cc. The high MW fraction preferably has a higher or higher comonomer content than the lower MW fraction. In particular, preferably, the HMW fraction has at least 10% by weight greater than the LMW grade, preferably at least 15% by weight and more preferably at least 20% by weight. One of the total monomer content. The above elastomers provide optimum rheology for dispersion in PP and optimum MWD for impact modification.

Preferably, the elastomer has a bimodal molecular weight distribution comprising greater than 50% by weight of the HMW fraction and having a difference in comonomer content of at least 10% by weight between the HMW fraction and the LMW grade.

The MMWD elastomer can be made by any number of methods, included in a single reactor or in situ in a cascaded cascade reactor, or blended by a post reactor. Any polymerization medium can be used, including solutions, slurries, or gas phases. The multimodal distribution elastomer can be part of a cascaded cascade reactor in the reactor which is a blended copolymer of predominantly polypropylene. Preferably, it can be made in a single reactor using a two-post metallocene catalyst, one of which is a LMW grade, and one of which is a HMW grade. A method of making an MMWD elastomer can be found, for example, in International Application Publication No. WO2002/074816. Suitable catalysts are disclosed in, for example, International Publication No. WO 2012/027448 and U.S. Patent Application Publication No. 2011/0282018.

Preferably, the elastomeric system is present in an amount from 15% to 30% by weight, preferably from 16% to 27% by weight, and more preferably from 18% to 25% by weight, based on the total weight of the composition.

Block complex compatibilizer

The term "block copolymer" or "segmented polymer" refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") that are bound in a linear manner, ie Containing end-to-end versus polymerized functionality rather than by drape or grafting (covalent Bonding a polymer of one of the chemically distinct units. In a preferred embodiment, the content or type, density, amount of crystallization, crystalline form (eg, polyethylene to polypropylene) of the comonomers enclosed therein are attributable to one of the compositions The crystal size, degree or degree of stereoregularity (same row or row), regional regularity or regional irregularity, amount of branching (including long chain branches or hyperbranches), homogeneity, or any other chemistry Or physical properties are different. The block copolymer of the present invention is characterized by a unique distribution of both polymer polydispersity (PDI or Mw/Mn) and block length distribution, which in a preferred embodiment is due to a fusotropic agent in combination with a catalyst. effect.

The term "block composite" is meant to include a soft copolymer (wherein the comonomer content is greater than 10 mole percent and less than 90 mole percent, and preferably greater than 20 mole percent and less than 80 mole percent And an optimum system is greater than 33 mol% and less than 75% by weight of the polymerized unit), a hard polymer (wherein the monomer content is greater than 90 mol%, and preferably greater than 93 mol%, and More preferably, the amount is greater than 95% by mole, and the optimum is greater than 98% by mole, and a block copolymer (preferably a diblock having a soft segment and a hard segment) a polymer wherein the hard segment of the block copolymer is substantially the same composition as the hard polymer of the block composite, and the soft segment of the block copolymer and the soft copolymer of the block composite are substantially The same composition. The block copolymer can be linear or branched. More particularly, when manufactured in a continuous process, the block composite is desirably from 1.7 to 15, preferably from 1.8 to 3.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. PDI. When manufactured in a batch or semi-batch process, the block composite is desirably from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and preferably from 1.4 to 1.8. PDI. Block compound It is described in, for example, U.S. Patent Application Publication Nos. US 2011-0082257, US 2011-0082258, and US 2011-0082249, all of which are published on Apr. 7, 2011, and are related to block composites, methods for their manufacture, and The description of the analytical method is incorporated herein by reference. In particular, in the case of co-single system ethylene, it is preferably from 10 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, and the optimum is from 33 mol. % to 75 mol% is present. Preferably, the copolymer comprises a hard segment of from 90 mole percent to 100 mole percent propylene. The hard segment can be greater than 90 mole percent, preferably greater than 93 mole percent, and more preferably greater than 95 mole percent propylene, and most preferably greater than 98 mole percent propylene. These hard segments have a relative melting point of 80 ° C and higher, preferably 100 ° C and higher, more preferably 115 ° C and higher, and preferably 120 ° C and higher. Additionally, the block composite preferably has a Tm greater than 100 ° C, preferably greater than 120 ° C, and preferably greater than 125 ° C. Preferably, the block composite has an MFR of from 0.1 to 1000 dg/min, more preferably from 0.1 to 50 dg/min, and even more preferably from 0.1 to 30 dg/min. Further, the block composite of this embodiment of the invention has a weight of from 10,000 to about 2,500,000, preferably from 35,000 to about 1,000,000, and more preferably from 50,000 to about 300,000, preferably from 50,000 to about 200,000. Average molecular weight (Mw).

"Hard" segmentation refers to a high crystalline block of a polymerization unit wherein the single system is greater than 90 mole percent, and preferably greater than 93 mole percent, and more preferably greater than 95 mole percent, and The optimum system is present in an amount greater than 98% by mole. In other words, the comonomer content in the hard segment is preferably less than 2 mol%, and more preferably less than 5 mol%, and preferably less than 7 mol%, and less than 10 mol%. . In certain embodiments, the hard segment comprises all or substantially all of the propylene units. The other side By "soft" segment, the amorphous, substantially amorphous, or elastomeric block of the polymerization unit, wherein the comonomer content is greater than 10 mol% and less than 90 mol%, And preferably more than 20% by mole and less than 80% by mole, and the optimum is greater than 33% by mole and less than 75% by mole.

Preferably, the block composite and the crystalline block complex polymer comprise a catalyst comprising an addition polymerizable monomer or a monomer mixture under an addition polymerization reaction reaction condition comprising at least one addition polymerization catalyst. The catalyst is prepared by contacting one of the components of the one-chain shuttle agent, the method is characterized by one of two or more reactors operating under steady state polymerization conditions, or one of the operations under plug flow polymerization conditions At least some of the growing polymer chains are formed under different processing conditions in two or more regions of the reactor. In a preferred embodiment, the block composite of the present invention comprises a block polymer fraction having one of the largest possible distributions of block lengths.

A suitable method for the manufacture of the block composites and the crystalline block composites can be found, for example, in U.S. Patent Application Publication No. 2008/0269412, issued Oct. 30, 2008, which is incorporated herein by reference. In this case, I think it is a reference. In particular, the polymerization reaction is preferably carried out by a continuous polymerization reaction, preferably a continuous solution polymerization reaction in which a catalyst component, a monomer, and a selective solvent, an adjuvant, a scavenger, and a polymerization reaction are carried out. The adjuvant is continuously supplied to one or more reactors or zones and the polymer product is continuously removed therefrom. In this context, the terms "continuous" and "continuously" are used to intermittently add reactants and remove products at small or irregular intervals, such that over time, the overall process is essentially Continuous method. Furthermore, as explained before, the chain shuttle agent can be polymerized Addition at any point during the period, included in the first reactor or zone, either slightly upstream of the outlet or at the first reactor outlet, or between the first reactor or zone and the second or any subsequent reactor or zone. Due to the difference in monomer, temperature, pressure or other differences in polymerization conditions between at least two reactors or zones connected in series, different compositions (such as comonomer content, crystallinity, Polymer segments of density, stereoregularity, regional regularity, or other chemical or physical differences are formed in different reactors or zones. The size of each segment or block is determined by the conditions of the continuous polymerization reaction, and preferably the polymer size is most likely to be distributed.

Preferably, the block composite is from 3% by weight to 15% by weight, preferably from 5% by weight to 10% by weight, and more preferably from 6% by weight to 9% by weight, based on the total weight of the composition. The quantity exists.

Additives and fillers

Such as antioxidants (e.g., hindered phenol resin (e.g., Irganox ^TM 1010), phosphites (e.g., Irgafos ^TM 168)), adhesive additives (e.g., the PIB), anti-caking additives, colorants, fillers (e.g., Additives such as talc, diatomaceous earth, nanofiller, clay, metal particles, glass fibers or granules, carbon black, other reinforcing fibers, and the like may also be included in the formulation. Preferably, the composition comprises talc in an amount of from 0% by weight to 35% by weight, from 1% by weight to 25% by weight and more preferably from 5% by weight to 25% by weight, based on the total weight of the polymer. Other additives may be present in an amount from 0.01% to 1% by weight.

Application and end use

Useful manufacturing articles or parts that can be uncovered from here Manufactured using a variety of methods, including various injection molding methods (for example, in Modern Plastics Encyclopedia/89, issued October, 1988, Vol. 65, No. 11, pp. 264-268, "Introduction to Injection Molding") Pp. 270-271, "Injection Molding Thermoplastics", the disclosures of which are hereby incorporated by reference in its entirety in the entire entire entire entire entire entire entire entire entire entire entire entire content Vol. 65, No. 11, pp. 217-218, "Extrusion-Blow Molding", the disclosure of which is hereby incorporated by reference in its entirety in its entire entire entire entire entire entire entire entire entire entire entire content Some of these manufactured articles include fuel tanks, outdoor furniture, pipelines, automotive container applications, automotive bumpers, signage, rim covers and grilles, and other household and personal items, including, for example, chiller containers. Of course, those skilled in the art can also combine polymers to advantageously use refractive index to improve or maintain the clarity of end use articles such as chiller containers.

testing method

Density is measured in accordance with ASTM D 792.

Differential Scanning Calorimetry (DSC) was performed on a compression molded sample using a TA Instruments Q100 or Q1000 DSC and a clip-sealed Perkin Elmer disk. The sample was equilibrated at -90 ° C for 5 minutes, then heated to 180 ° C at 10 ° C / min (take "first heating DSC curve") for 5 minutes, then cooled to -90 ° C at 10 ° C / minute (撷The "crystallization curve" was taken for 5 minutes, and then heated to 180 ° C at 10 ° C / minute (take "second heating DSC curve"). The data was analyzed using the TA Universal Analysis software after the operation was completed.

The melt flow rate of the sample was measured using ASTM D 1238, condition 230 ° C, 2.16 kg. The melt index or I ₂ system was measured using ASTM D 1238, condition 190 ° C, 2.16 kg. The melt flow rate of the sample was measured using ASTM D1238, condition 230 ° C, 10 kg. The melt index or I ₁₀ system was measured using ASTM D 1238, condition 190 ° C, 10 kg.

¹³ C NMR analysis

The sample was added to a 0.4 gram sample in a 10 mm NMR tube by approx. 3 grams of a 50/50 mixture of tetrachloroethane-d ² /o-dichlorobenzene. The sample was dissolved and homogenized by heating the tube and its contents at 150 °C. Data line using a JEOL Eclipse ^TM 400MHz spectrometer or a Varian Unity Plus ^TM 400MHz proposed spectrum collected, which corresponds to line ¹³ C resonance frequency of 100.5MHz. The data was obtained using 4000 transients and 6 second pulse repetitions per data file. To achieve the minimum signal-to-noise ratio for quantitative analysis, several data files are added together. The spectral width is 25,000 Hz, and the smallest file of 32K data points. Samples were analyzed at 130 ° C on a 10 mm wide band probe. Co-monomers are used in the Randall triad method (Randall, JC; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which is hereby incorporated by reference in its entirety.

HTLC

The high temperature liquid chromatography (HTLC) is carried out according to the method disclosed in the U.S. Patent Application Publication No. 2010-0093964 and the U.S. Patent Application Serial No. 12/643,111, filed on Dec. 21, 2009, both. This article is incorporated herein by reference. Samples were analyzed by the means described below.

Combined with a Waters GPCV2000 high temperature SEC chromatography to build HT-2DLC instrument configuration. The two Shimadzu LC-20AD pumps were connected to the syringe valve of the GPCV2000 via a binary mixer. The first dimension (D1) HPLC column was connected between a syringe and a 10-well switching valve (Valco Inc). The second dimension (D2) SEC column is connected between a 10-well valve and a LS (Varian Inc.), IR (concentration and composition), RI (refractive index), and IV (intrinsic viscosity) detector. Built-in detector for RI and IV GPCV2000. The IR5 detector was supplied by PolymerChar, Valencia, Spain.

Column: The D1 column was purchased from a high temperature Hypercarb graphite column (2.1 x 100 mm) from Thermo Scientific. The D2 column was purchased from one of the Varian's PLRapid-H columns (10 x 100 mm).

Reagents: HPLC grade trichlorobenzene (TCB) was purchased from Fisher Scientific. 1-nonanol and decane were obtained from Aldrich. 2,6-Di-t-butyl-4-methylphenol (Ionol) was also purchased from Aldrich.

Sample preparation: 0.01-0.15 grams of the polyolefin sample was placed in a 10-mL Waters automatic take-up machine vial. 7-ml of 1-nonanol or decane with 200 ppm Ionol was then added to the glass vial. After spraying helium gas into the sample glass bottle for about 1 minute, the sample glass bottle was placed on a heated vibrator having a temperature set at 160 °C. The dissolution was carried out by shaking the glass bottle at this temperature for 2 hours. The vial is then transferred to an autosampler for injection. Please note that due to the thermal expansion of the solvent, the actual volume of the solution is more than 7 ml.

HT-2DLC: D1 flow rate is 0.01 ml/min. For 10 minutes before this operation, the composition of the mobile phase was a 100% weak eluent (1-nonanol or decane). Then, at 489 minutes, the composition was increased to a 60% strong eluent (TCB). Data were collected for 489 minutes during the original chromatogram. 10-hole valve per Three minute switching resulted in a 489/3 = 163 SEC chromatogram. The post-operation gradient was used after 489 minutes of data acquisition to clean and balance the column for the next operation.

Cleaning steps:

1. 490 minutes: flow = 0.01 minutes; / / maintain a fixed flow rate of 0.01 ml / minute from 0-490 minutes.

2. 491 minutes: flow = 0.20 minutes; / / flow rate increased to 0.20 ml / minute.

3. 492 minutes: %B=100; / / mobile phase composition increased to 100% TCB

4. 502 minutes: % B = 100; / / use 2 ml TCB cleaning column

Balance step:

5. 503 minutes: %B = 0; / / make the mobile phase composition into 100% 1-nonanol or decane

6. 513 minutes: %B=0; // use 2 ml of weak eluent to balance the column

7. 514 minutes: flow = 0.2 ml / min; / maintain a fixed flow of 0.2 ml / min from 491-514 minutes

8. 515 minutes: flow = 0.01 ml / min; / / reduce the flow rate to 0.01 ml / min.

After step 8, the flow rate and mobile phase composition are the same as the starting conditions of the operating gradient.

The D2 flow rate was at 2.51 ml/min. Two 60 μL loops were mounted on a 10-hole switching valve. A 30-μL eluate from the D1 column was loaded onto the SEC column with each switch.

IR, LS15 (light scattering signal at 15°), LS90 (light scattering signal at 90°), and IV (intrinsic viscosity) signals are transmitted by EZChrom SS420X analogy digital box change collection. The chromatogram is output in ASCII format and input from a MATLAB software for data reduction. The curve was appropriately corrected using one of the polymer composition and the retention volume, and a polymer having a similar property to the hard block and the soft block contained in the block composite was analyzed. The composition of the calibration polymer (molecular weight and chemical composition) needs to be narrow and span a reasonable molecular weight range to encompass the composition of interest during the analysis. The analysis of the raw data was calculated as follows. The first dimension HPLC chromatogram was reconstructed by plotting the IR signals for each of the plots as a function of the elution volume (from the entire IR SEC chromatogram of the cut plot). The IR-to-D1 elution volume is normalized by all IR signals, and a graph of gravimetric analysis versus D1 elution volume is obtained. The IR methyl/measurement ratio was obtained from the reconstructed IR measurements and IR methyl chromatograms. This ratio was converted to a composition using a PP weight percent (by NMR) versus methyl/measured calibration curve obtained from the SEC experiment. The MW series was obtained from the reconstructed IR and LS chromatograms. This ratio is converted to MW using PE standards after calibration of the IR and LS detectors.

HT GPC

A high temperature gel permeation chromatography system (GPC IR) consisting of an infrared concentration detector (IR-4) from PolymerChar Inc (Valencia, Spain) is used for molecular weight (MW) and molecular weight distribution (MWD) Decide. The carrier solvent is 1,2,4-trichlorobenzene (TCB). The autosampler compartment was operated at 160 °C and the column compartment was operated at 150 °C. The column used was four Polymer Laboratories Olexis, 13 micron columns. The chromatographic solvent (TCB) and sample preparation solvent were from the same solvent source, with 250 ppm of butylated hydroxytoluene (BHT) and sparged with nitrogen. The sample is based on 2 mA in the TCB. Prepared at a concentration of grams per milliliter. The polyethylene sample was gently shaken at 160 ° C for 2 hours. The injection volume was 200 μl and the flow rate was 1.0 ml/min.

Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards. The standards have molecular weights ranging from 580 to 8,400,000 g/mole and are configured in 6 "cocktail" mixtures with at least ten separations between individual molecular weights.

The polystyrene standards peak molecular weight was converted to polyethylene molecular weight using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M _polyethylene = A ( M _polystyrene ) ^B (1) Here, B has a value of 1.0, and the experimental value of A is about 0.39.

A first-order polynomial is used to fit the individual polyethylene equalization correction points obtained from equation (1) to the observed elution volume of the polystyrene standards.

The quantity, weight, and z-average molecular weight are calculated according to the following equation: Wherein, Wf _i is the weight fraction of the i component, and M _i is the molecular weight of the i component.

MWD is expressed by the ratio of the weight average molecular weight (Mw) logarithmic average molecular weight (Mn).

Accurate A value is adjusted by adjusting the value of A in equation (1) to the user. The Mw calculated by the formula (3) and the corresponding retention volume polynomial is determined by the coincidence of the known Mw value of 115,000 g/mole of a standard linear polyethylene homopolymer reference.

GPC deconvolution

The GPC data is deconvoluted to produce the largest possible fit of the two molecular weight components. There are many deconvolution calculations available in the literature. These assumptions based on usage lead to different answers. The calculations reviewed here are best for the inverse of the two largest possible molecular weight distributions (plus an adjustable error term). To allow for variations in the base distribution due to small fluctuations in macromonomer and reactor conditions (i.e., temperature, concentration), the basis function is modified to incorporate a normal distribution term. This makes the basic function of each component "blurred" to varying degrees along the molecular weight axis. The advantage is this limit (low LCB, full concentration, and temperature control), and the basic function becomes a simple and maximum possible Flory distribution.

The three components (j = 1, 2, 3) are derived from the third component of the adjustable error term (j = 3). GPC data needs to be normalized and appropriately converted to a weight fraction versus Log ₁₀ molecular weight vector. In other words, each possible curve of the deconvolution is composed of a height vector, h _i , where the height is reported at a known interval of the Log ₁₀ molecular weight, and h _i has been appropriately converted from the elution volume to the Log ₁₀ molecular weight. Domain, and h _i is normalized. In addition, such data is required for use in Microsoft EXCEL ^TM applications.

Several hypotheses are made in the inverse product. Each component, j, consists of a maximum possible Flory distribution that has been deconvoluted with a regular or Gaussian extension function using a parameter σ _j . The three basic functions formed are for Chi-square, X ² , minimizing the program to locate the parameters that best fit the n points of h _i , the GPC data vector.

The variable, CumND _j,k , is calculated using the EXCEL ^TM function "NORMDIST (x, average, standard deviation, cumulative)" as follows: x = μ _j + (k - 10) * σ _j / 3

Average = μ _j

Standard deviation = σ _j

Cumulative = TRUE

Table I below summarizes the definitions of these variables and their equivalents. EXCEL ^TM software application, Solver, the use of a suitable system for this job. Limits are added to Solve to ensure proper minimization.

The eight parameters derived from the chi-square minimization are μ ₁ , μ ₂ , μ ₃ , σ ₁ , σ ₂ , σ ₃ , w ₁ , and w ₂ . The w ₃ term is derived from w ₁ and w ₂ since the sum of the 3 components needs to be equal to 1. Table II summarizes the Solver limitations for the EXCEL program.

Additional limitations to be understood include a limitation that only allows μ _j >0, even if Solver is properly initialized, this limitation need not be included because the Solver program does not shift any μ _{j by at} least about 0.005. Furthermore, w _j needs to be understood to be positive. This limit can be handled outside of Solver. If w _j is understood to be generated by selecting two points along the interval 0.0 < P ₁ < P ₂ <1.0; therefore, w ₁ = P ₁ , w ₂ = P _{2 -} P ₁ , and w ₃ = 1.0-P _2; lines P1 and P2 is restricted equal to the limit of the desired above for w _j.

Table III is an overview of the Solver settings for the Options tab.

The first guess of the values of μ ₁ , μ ₂ , w ₁ , and w ₂ can be obtained by assuming a two ideal Flory component, which provides an observed weight average, number average, and z-average molecular weight of the observed GPC distribution. .

w ₁ + w ₂ =1

Then, the values of μ ₁ , μ ₂ , w ₁ , and w ₂ are calculated. Before entering the Solver of the minimization step, these values need to be carefully adjusted to allow for small error terms, w ₃ , and to meet the limits in Table II. The starting value of σ _j is set to 0.05. The octene content was determined from HT GPC IR: The octene content was determined using an IR-5 composition detector of Polymer Char Inc. The composition detector uses 11 ethylene/octene (EO) copolymers and a polyoctene (PO) homopolymer (100% by weight) made of a metallocene solution having a weight percentage of from 0 to 40 octene. Octene) correction. All polymers have individual Mw of about 40K or 100K. The signal at the peak position is used for correction. The linearity of the octene weight % to the IR-5 methyl/methylene signal ratio is established for these EO copolymers and PO polymers.

The octene weight percent distribution of the resin was obtained by linear correction using IR-5 methyl/methylene signal and octene weight % and IR-5 methyl/methylene signal ratio. The final efficacy of the polymer chain is collected at the end of the ethylene chain.

For bimodal resins, the weight percent of octene in each fraction is calculated as follows. For the high weight fraction (main peak), the octene weight % is calculated using the flat zone of the distribution curve of the main peak region. For low weight fractions (small peaks), the octene weight % is calculated over a narrow MW range (0.3 on the log MW scale) to avoid major peak contamination and ends with the elution of low concentrations of scattered octene weight % signal .

Izod impact test

The notched Izod impact test was performed on an injection molded ASTM specimen having a size of 62 mm x 19 mm x 3.175 mm from a tensile rod cut. The sample was cut using a slotting device in accordance with ASTM D256, resulting in a depth of cut of 10.16 ± 0.05 mm. Five samples per sample were tested at 23 °C using ASTM D256. If the energy value of KJ/m ² is reported, the energy value reported in KJ/m ² is derived by multiplying the energy value of 呎-lb/mile by the conversion factor of 5.25.

Flexural modulus

The flexural modulus test was performed on a 5 unit United flexible frame in accordance with ISO 178 at 2.5 mm and 50% relative humidity for 40 hours, using a span of 2.5 inches at 2 mm/min according to ISO 178. The chordwise modulus is reported for stress values of 0.5 and .25% strain. The mean and standard deviation are reported.

Viscosity and viscosity ratio (P)

The dynamic mechanical spectroscopy (DMS) of the material was obtained using an ARES II rheometer from TA Instruments. The rheometer was equipped with a parallel plate of 25 mm diameter, and the gap between the plates was set to 2 mm. All measurements were carried out at 190 ° C with a step of changing from 100-0.1 rad/s with 10% strain. P is defined as the viscosity in the dispersion-based elastomer of 100s ^-1 at phase divided by the viscosity of the PP 100s ^-1 of the matrix phase.

Atomic Force Microscopy (AFM) - Area Weighted Mean Diameter (Da) (micron) Measurement

Compressed molded sheets of each blend were used for AFM imaging. A small portion of the compression molded sheet was sliced at a low temperature of -120 ° C to produce a polished block surface. A Dimension 3100 DI/Veeco AFM is used for phase detection in the tap mode. Operate the soft system v7.30. The tip for all scans has a resonance frequency of ~170 khz and a MikroMasch NCS #16 with a spring constant of 40 N/m. Image analysis was performed on five 60 x 60 mm ² scans to obtain a particle size distribution for each blend. Area weighted average diameter (D _a ): Wherein, A _i is the area of each particle; D _i is the diameter of each particle.

example MMWD Elastomers Examples 1-3 and Comparative Examples C1 and C2

For Examples 1-3 and Comparative Examples 1-2, a cocatalyst having a singular formula of ((C _14-18 H _27-35 ) ₂ CH ₃ N] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- Tallow alkyl) methylammonium tetrakis(pentafluorophenyl)borate is used in a ratio of 1.2 to 1 mole with the catalyst. The cocatalyst system was purchased from Boulder Scientific and used without further purification.

Catalyst A is dimethyl [[2',2'''-[1,3-propanediylbis(oxy-κO)] bis[3-[3,6-bis(1,1-dimethyl B) -9H-carbazole-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-alcohol It is prepared as described in Example 1 of WO2012027448. Catalyst B is dimethyl [[2',2'''-[1,3-propanediylbis(oxy-κO)] bis[3-[3,6-bis(1,1-dimethyl B) -9H-carbazol-9-yl]-3',5'-difluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]- 2-Alcoholate-kappaO]](2-)]-oxime and can be prepared according to Example 1 of US20110282018. Catalyst C is dimethyl [[2',2'''-[1,3-propanediylbis(oxy-κO)] bis[3-[3,6-bis(1,1-dimethyl B) -9H-carbazole-9-yl]-5'-fluoro-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]-2-alcohol The complexes Q1 and ZrCl _{4 which} are disclosed in WO2012027448 are prepared in a manner similar to the synthesis of Catalyst A. For all of the examples, the cocatalyst was used at a molar ratio of 1.2 to 1 with the catalyst.

Comparative Examples 3, 4, and 5 were 1.6% BSA (ENGAGE 8407), ENGAGE 8200, and ENGAGE 8100, respectively.

Preparation of block composite

Catalyst-1 ([[rel-2',2'''-[(1R,2R)-1,2-cyclohexanediylbis(methyleneoxy-κO)] bis[3-(9H-咔) Azole-9-yl)-5-methyl[1,1'-biphenyl]-2-alcohol-κ O]](2-)]dimethyl-anthracene) and co-catalyst-1 (four the borate methylenebis (C _14-18 alkyl) ammonium salt mixture (pentafluorophenyl) substantially as USP 5,919,983, example 2 disclosed, with a long chain trialkylamine (Armeen ^TM M2HT, available Prepared from Akzo-Nobel, Inc., HCl and Li[B(C ₆ F ₅ ) ₄ ] reaction was purchased from Boulder Scientific and used without further purification.

CSA-1 (diethylzinc or DEZ) and cocatalyst-2 (modified methylaluminoxane (MMAO)) were purchased from Akzo Nobel and used without further purification. The solvent for the polymerization reaction was obtained from a hydrocarbon mixture (ISOPAR ^® E) from ExxonMobil Chemical Company and purified via a 13-X molecular sieve bed prior to use.

The block complex of this example is referred to as BC. It was prepared using two continuous stirred tank reactors (CSTR) connected in series. The first reactor volume is about 12 gallons and the second reactor is about 26 gallons. Each reactor is fully hydraulic and is set to operate in steady state conditions. Monomer, Solvent, Hydrogen, Catalyst-1, Cocatalyst-1, Cocatalyst-2 and CSA-1 were fed to the first reactor according to the treatment conditions outlined in Table 2. The first reactor contents described in Table 2 were streamed to a second reactor in series. Further monomer, solvent, hydrogen, catalyst-1, cocatalyst-1, and selective cocatalyst-2 are added to the second reactor.

The BSA coupling of ENGAGE 8407 POE (polyolefin elastomer) was carried out by melt blending with Coroion WP-30ZSK, one of 100 RPM speeds, with a twin-screw extruder. To reduce chain scission during melt blending, Molecular Melt (DPO-BSA) powder is used as a source of BSA. It has a ratio of 3.3 parts of IRGANOX 1010 to 1 part of BSA. 1.6% by weight of molecular melt and ENGAGE 8407 by using the above The method melt blends to form a BSA modified POE with MI 1.1.

Blend PP/MWMD Elastomer/BC Sample Ingredient and Injection Molding

All components were dry tumbling and direct blending using a Leistritz micro-18 twin screw extruder or a ZSK-25 twin screw extruder. The injection molded ASTM D-638 Type I tensile bar was obtained for mechanical testing using an Arburg 370 C injection molding machine.

1, 2 and 3 show the inversely folded HT-GPC diagrams of Examples 1, 2, and 3 of the present invention. As can be seen, the elastomer of the present invention exhibits a true bimodal molecular weight distribution and composition distribution. As described above in the test method, the GPC curve can be deconvoluted to approximate the individual average molecular weight distribution and grade of each peak. Table 3 shows the molecular weights determined from this deconvolution method. As shown, each peak of each of the inventive examples has a range of molecular weights and distributions. For example, Example 1 of the present invention contains 81.6% by weight of 132,291 A high molecular weight fraction of Mw from Dalton. In another aspect, Example 3 of the present invention contains 61.6% by weight of a high molecular weight fraction having a Mw of 216,526 Daltons. In Examples 1-3, the higher molecular weight mode is the primary composition and has a higher comonomer 1-octene content. In addition, the difference in comonomer 1-octene content between the LMW and HMW modes is at least 20% by weight. Comparative Example C1 exhibited a monomodal molecular weight and composition distribution on the upper layer. Comparative Example C2 exhibited a bimodal molecular weight and composition distribution. However, the difference in comonomer 1-octene content between the two modes is less than 10% by weight. Furthermore, the HMW mode consists of less than 30% by weight of the total composition.

Comparative Example C3-C5 was produced via standard commercial single catalyst, single reactor fabrication, and exhibited a substantially monomodal molecular weight distribution.

As seen in Table 9, when blended in polypropylene in equal amounts, Comparative Examples C1-C5 for comparison of Blend Blend C1-blend C5 were used for the example blending of the present invention. Examples 1, 2, and 3 of the blend of Compound 1 - Blend 3 exhibit similar or somewhat better impact toughness. However, when combined with the block complex (BC), the impact modifier of the present invention for use in the blend blend 1-BC-blend 3-BC of the present invention is used as an example 1-3. To have a strong multiplicative toughening effect, which is sufficient to exceed the comparative examples C1-C5 for comparing the blended compound C1-BC-blend C5-BC. Further, as shown in Table 9, when evaluating the viscosity ratio (P) of the elastomer to the matrix polypropylene, the general tendency suggests that the elastomer particle size (Da) reasonably satisfies the viscosity ratio (P). Thus, overall, lower P produces a lower elastomer particle size Da. When the block complex (BC) is added to these elastomers as part of the blend composition, a large change in particle size is observed. Chemical. This was previously confirmed in U.S. Patent Application Serial No. US2011/0082257.

However, it can be seen that the elastomer particle size does not need to follow the impact toughness. For example, Comparative Examples C3 and C3-BC individually exhibited lower particle sizes than Examples 1, 2 and 1-BC, 2-BC of the present invention. Comparative Examples C3 and C3-BC exhibited comparable particle sizes compared to Examples 3 and 3-BC of the present invention.

For the impact strength results, the comparative blend C3 exhibited higher impact toughening than the example blends 1 and 2 and 3. However, the exemplary blends 1-BC, 2-BC, and 3-BC produced significantly higher impact toughening than the comparative blend C3-BC when blended with the block composite BC. While not wishing to be bound by any theory, it is believed that the high molecular weight fraction of the elastomer impact modifier can play an important role in impact toughening at significantly lower elastomer particle size (Da). In this case, it has been observed that blending in a batching apparatus such as a twin-screw extruder, the low molecular weight (LMW) fractions of Examples 1, 2, and 3 of the present invention enable the elastomer to have a minimum shear rate (100 rad/ Sec) exhibits a low enough viscosity to achieve a low elastomer particle size (Da). If Table 3 is observed and HMW wt% is subtracted from 100, an approximate value for the LMW wt% fractionation is obtained. Using the difference, the LMW weight percentages of Examples 1, 2, and 3 were calculated to be 18.4, 30.3, and 38.4%. The increase in LMW results in a lower P and a lower Da. As shown in Table 9, the addition of the block composite BC can additionally reduce Da. From Table 2, if the comparative examples of Mw and Mz of Examples 1, 2 and 3 of the present invention, it is noted that the lines are significantly higher than Comparative Example C3, and the numerical values are increased from Examples 1 to 3. Further, it is noted from Table 3 that the Mw and Mz of the HMW fraction of the exemplary elastomer of the present invention are increased from Examples 1 to 3, and therefore, it is noted that there is an LMW fraction in any of the examples of the present invention. And the block copolymer BC of the highest Mw and Mz, when blended with Example 3, produced the exemplary blend 3-BC of the present invention exhibiting the highest impact strength of any of the compositions in Table 9. In Table 10, Example 3 of the present invention used in the example blend 3 exhibited a similar to slightly higher impact toughening than Comparative Example C3 or C5 for the comparative blends C3 and C5 polypropylene. . When combined with the block complex BC, this produced the inventive blend 3-BC, exhibiting more than twice the impact strength of the comparative blend C3-BC-1 or C5-BC. The comparison blend C3-BC-2 compared the repeat of the blend C3 BC-1 and again produced the impact results of the comparative blend C3-BC-1. The performance of Example 3 of the present invention is further exemplified when combined with talc. The performance of Example 3 of the present invention for Example 3-T showed similar performance compared to Comparative Example C3 used for the example blend C3-T, and was slightly less than Comparative Example C5 for the example blend C5-T. Higher performance. However, when combined with the block complex BC, the formed blend of the invention 3-BC-T-1 exhibits a proximity to the comparative blend C3-BC-T or the comparative blend C5-BC-T. Double impact performance. The blend 3-BC-T-2 of the present invention is a repeat of the blend 3-BC-T-1 of the present invention, and again produces the impact of the blend of the present invention 3-BC-T-1.

Claims (3)

A composition comprising: polypropylene; and a multimodal molecular weight distribution elastomer; a block composite; and a selective filler wherein the multimodal molecular weight distribution elastomer has a high molecular weight fraction and a low molecular weight fraction And a low molecular weight fraction of the multimodal molecular weight distribution elastomer having a molecular weight of from 5 kg/mol to 50 kg/mol, wherein the high molecular weight fraction of the multimodal molecular weight distribution elastomer has a molecular weight greater than the multimodality The low molecular weight fraction of the distributed elastomer is at least 10% by weight of one comonomer content, and wherein the block composite comprises a soft copolymer, a hard polymer and a block copolymer, and the block copolymerization The material has a soft segment and a hard segment, wherein the hard segment of the block copolymer is the same as the hard polymer of the block composite, and the soft segmentation of the block copolymer is combined with the block. The composition of the soft copolymer is the same. The composition of claim 1, wherein the high molecular weight fraction has a molecular weight of from 75 kg/m to 600 kg/mole. The composition of claim 1, wherein the high molecular weight fraction of the multimodal molecular weight distribution elastomer has a comonomer content of at least 20% by weight greater than the low molecular weight fraction of the multimodal molecular weight distribution elastomer. .