• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to impact resistant copolymer compositions of polypropylene which exhibit increased rigidity without reducing the impact resistance properties. The copolymers of impact resistant polypropylene comprise a matrix and a dispersed phase. The matrix comprises a homopolymer of polypropylene or a random copolymer of propylene / alpha-olefin which comprises more than 50% by weight of units derived from propylene monomer. The matrix should have a relatively high crystallinity, preferably 50% or higher. The polypropylene homopolymer or the propylene / alpha-olefin random copolymer preferably has a MWD greater than 4 to about 7, as typically obtained using Ziegler-Natta catalysts. The dispersed phase of the impact resistant copolymer comprises an ethylene-propylene copolymer comprising from 45 to 65% by weight of units derived from an ethylene monomer. Preferably, the dispersed phase comprises from about 30 to 50% by weight of the impact resistant copolymer of polypropylene.
    公开号:SE537777C2
    申请号:SE1350016
    申请日:2011-06-06
    公开日:2015-10-13
    发明作者:Chai-Jing Chou
    申请人:Grace W R & Co；
    IPC主号:
    专利说明:

    [1] This application seeks priority from U.S. Utility Patent Application No. 12 / 797,717, filed June 10, 2010, and is incorporated herein by reference in its entirety.
    [2] The present invention relates to impact copolymers of polypropylene with improved rigidity and good impact properties.
    [3] Impact-bearing copolymers (ICPs) of propylene are commonly used in a variety of applications where strength and impact resistance are preferred such as cast and extruded car parts, household appliances, luggage and furniture.
    [4] Homopolymers of propylene or propylene-based random copolymers having a high crystallinity are often unsuitable for such applications themselves because they are too sparse and have low impact, while impact copolymers are specifically designed for applications such as these.
    [5] Impact propylene copolymers are typically an integral blend of a continuous phase of crystalline propylene homopolymer or random copolymer and dispersed rubber phase of ethylene-propylene copolymer. In general, the continuous phase is known to provide properties such as stiffness and the dispersed phase provides impact properties.
    [6] In general, it has been observed that the stiffness properties, and impact, move in the opposite direction so that stiffness increases, impact decreases and vice versa. It is desirable to develop compositions which exhibit improved stiffness without deterioration of impact.
    [7] The present invention relates to such a composition. One aspect of the present invention specifically relates to a copolymer of an impact propylene: a matrix and a dispersed phase. The matrix comprises a homopolymer of polypropylene or a random copolymer of propylene / alpha-olefin which comprises up to 50% by weight of units derived from propylene monomer. The matrix should have a relatively 1,537,777 high crystallinity, preferably 50% or more. The homopolymer of polypropylene or a random copolymer of propylene / alpha-olefin preferably has a MWD greater than 4 to about 7, which is usually obtained using Ziegler-Night catalysts. The dispersed phase of the impact copolymer comprises an ethylene-propylene copolymer comprising from 45 to 65% by weight of units derived from an ethylene monomer. Preferably, the dispersed phase comprises from about 30 to 50% by weight of the copolymer of impact propylene.
    [8] Unless otherwise indicated, the following analytical methods are used in the present invention: Bending modulus is determined according to ASTM D790-00 Method 1, using the ASTM D638 samples tested at 1.3 mm / min.
    [9] Molecular weights (Mn, Mw and Mz) and molecular weight distributions Mw / Mn (also called "MWD") and Mz / Mw are fed by GPC according to Gel Permeation Chromatography (GPC) Analytical Method for Polypropylene. The polymers are analyzed on a PL-220 series high temperature GPC unit equipped with a refractometer detector and four PLgel Mixed A columns (20 μm) (Polymer Laboratory Inc.). The oven temperature is 150 ° C and the temperature of the hot and hot zones of the automatic sample collector is 135 ° and 130 ° C respectively. The solvent is nitrogen deaerated 1,2,4-trichlorobenzene (TCB) containing -200 ppm 2,6-di-t-butylmethylphenol (BHT). The flow rate is 1.0 ml / min and the injection volume was 200 μl. A 2 mg / ml sample concentration is prepared by dissolving the sample in nitrogen purged and heated TCB (containing 200 ppm BHT) for 2.5 hours at 160 ° C with gentle stirring.
    [10] The GPC column set is calibrated using twenty narrow molecular weight distribution polystyrene standards. The molecular weight (Mw) of the standards ranges from 580 to 8,400,000 g / mol, and the standards in the containers were in 6 "cocktail blends". Each standard mixture has at least one decade separation between the individual molecular weights. The polystyrene standard is prepared with 0.005 g in 20 ml of solvent RV molecular weights equal to or greater than 2,537,777 at 1,000,000 g / mol and 0.001 g in 20 ml of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards are dissolved at 150 ° C for 30 minutes with stirring. The mixture of the narrow standards is crossed first and in descending order of maximum molecular weight to reduce the degradation effect. A logarithmic molecular weight calibration is created with a fourth order polynomial fit as a function of elution volume. The equivalent polypropylene molecular weights are calculated using the following equation with reported Mark-Houwink coefficients for polypropylene (Th. G. Sholte, NLJ Meijerink, HM Schoffeleers, and AMG Brands, J. Appl. Polym. Sci., 29, 3763-3782 (1984)). ) and polystyrene (EP
    [11] Izod toughness is assessed according to ASTM D 256.
    [12] Melt flow index (MFR) is fed according to ASTM D1238-01 test method at 230 ° C with a 2.16 kg weight for propylene based polymers.
    [13] The substances soluble in xylene (XS) are fed according to the following procedure: 0.4 g of polymer is dissolved in 20 ml of xylene with stirring at 130 ° C for 30 minutes. The solution is then cooled to 25 ° C and after 30 minutes the insoluble polymer fraction is filtered off. The resulting filtrate is analyzed by Flow Injection Polymer Analysis using a Viscotek ViscoGEL H-100-3078 column with THF mobile phase flowing at 1.0 ml / min. Column Or connected to a Viscotek Model 302 Triple 3 537 777 Detector Array, with light scattering, viscometer and refractometer detectors operating at 45 ° C. Instrument calibration is maintained with Viscotek P01yCALTM polystyrene standards.
    [14] Melting point is measured by DSC, ASTM D3418. Heat resistance (HDT) is rated according to ASTM D648.
    [16] An (total ethylene weight percent in the carbide copolymer of propylene) is measured by a select method reported by S. Di Martino and M. Kelchterman "Determination of the Composition of Ethylene-Propylene Rubbers Using 13 C-NMR Spectroscopy" J. of Applied Polymer Science, v 56, 1781-1787 (1995).
    [17] The amorphous rubber content of the basic copolymer can generally be determined by dissolving the basic copolymer in xylene. The amount of the substances soluble in the xylene mat by the Viscotek method (described above) plus 2% by weight corresponds to the amount of dispersed rubber phase (Fc) in the stable copolymer.
    [18] Ec (ethylene content in weight percent in the dispersed phase) is calculated as Ec = Et * 100 / Fc.
    [19] The basic copolymers of propylene (sometimes called ICPs) of the present invention comprise at least two major components, the matrix and the dispersed phase. The matrix preferably contains an isotactic homopolymer of propylene, although small amounts of a comonomer RV can be used to obtain special properties. Typically, such copolymers of the matrix contain 10% by weight or less, preferably less than 6% by weight or less, of comonomers such as ethylene, butene, 1-hexene or 1-octene. Most preferably less than 4% by weight of ethylene is used. The inclusion of comonomer typically results in a product with lower stiffness but with higher impact strength compared to degradable copolymers where the matrix is homopolymer of polypropylene.
    [20] The pitches of the matrix of the backbone copolymer can generally be determined from an analysis of the parts which are insoluble in the xylene of the backbone 4,537,777 copolymer composition, while the pitches of the dispersed phase can be attributed to the part which is soluble in the xylene.
    [21] The polymeric material used in the matrix of the state copolymer 5 of the present invention preferably has a relatively broad molecular weight distribution Mw / Mn ("MWD"), i.e. preferably greater than 4 to about 7, more preferably from 4.5 to 6. These molecular weight distributions are obtained in the absence of viscosity reduction (visbreaking) by the use of peroxide or other post-reactor treatment designed to reduce the molecular weight. Generally, polymers with higher MWD result in solid-state copolymers with higher stiffness but less static.
    [22] The matrix polymer preferably has a weight average molecular weight (Mw matt with GPC) of at least 200,000, preferably 300,000 and a melting point (Mp) of at least 145 ° C, preferably at least 155 ° C, more preferably 152 ° C, and most preferably at least 160 ° C. ° C.
    [23] Another important parameter of the matrix polymer is the amount of substances soluble in the xylene (XS) that they contain. The matrix polymer of the present invention may be characterized by having an added XS, preferably less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1.5% by weight.
    [24] The dispersed phase when used in the basic copolymers of the present invention comprises propylene / ethylene copolymer or the propylene / ethylene copolymer comprises from 45 to 65% by weight of units derived from an ethylene monomer. More preferably, the propylene / ethylene copolymer comprises from 50 to 65 weight percent units derived from an ethylene monomer. In some applications, it may be preferred that the propylene / ethylene copolymer comprise more than 50% of units derived from an ethylene monomer.
    [25] When used as the dispersed phase of the present invention, the propylene / ethylene copolymer has a molecular weight distribution Mw / Mn (MWD), of at least 2.5, preferably 3.5, and most preferably 4.5 or more. These molecular weight distributions should be obtained in the absence of viscosity reduction (visbreaking) or peroxide or other post-reactor treatment designed RV to 537 777 reduce the molecular weight. The propylene / ethylene copolymer preferably has a weight average molecular weight (Mw matt with GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
    [26] While these state-of-the-art polypropylene products can be manufactured by melt blending the individual polymer components, it is preferred that they be made in a reactor. This is conventionally accomplished by polymerizing propylene in a first reactor and transferring the high crystalline polypropylene from the first reactor to a second reactor where propylene and ethylene are copolymerized in the presence of the high crystalline material. Such "reactor-grade" products can theoretically interpolymerize in one reactor, but are more preferably made by using two reactors in series. The final impact copolymers are obtained from the reactor or reactors, however, may be mixed with various other components of other polymers.
    [27] The preferred narrow flow index ("MFR") of the cobblestone copolymer of the present invention depends on the end use but is typically in the range of from about 0.2 dg / min to about 200 dg / min, more preferably from about 5 dg / min. min to about 100 dg / min. Significantly, hog MFR, i.e. higher than dg / min are possible. MFR is determined by a conventional method such as ASTM1238 Cond. L (230 ° C / 2.16 kg). Another edge of salt to a hOg-MFR product involves chemical treatment, i.e. viscosity reduction (peroxide treatment) of a narrow PP heterophase copolymer. The state copolymers of the present invention generally comprise from about 80% to about 80% by weight of the matrix and from about 30% to about 50% by weight of the dispersed phase, preferably from about 60% to about 70% by weight of the matrix and from about 30% to about 40%. % of the dispersed phase.
    [28] The content of the overall comonomer (preferably ethylene) of the total base copolymer is preferably in the range of from about 10 ° A to about 35% by weight, more preferably from about 12% to about 28% by weight, and more preferably from about 15%. about 25% by weight of comonomer. 6 537 777
    [29] A variety of additives can be incorporated into the state copolymer for various purposes, such as those generally known in the art. Sanana additives include, for example, stabilizers, antioxidants, fillers, feedstocks, nucleating agents, and RV casting laxatives.
    [30] The bipolar copolymers of the present invention can be conventionally prepared by conventional polymerization processes such as a two-step process even if it is possible that they can be prepared in a single reactor. Each step can be performed independently in either the gas or liquid slurry phase.
    [31] In an alternative embodiment, the polymeric material used for the matrix in at least two reactors is obtained in order to obtain fractions with different melt flow indexes. This has been shown to improve the processability of the state copolymers.
    [32] As a general edge in the art, vale can be added to any of the reactors to control the molecular weight, intrinsic viscosity and melt flow index (MFR). The composition of the dispersed rubber phase is controlled (typically in the second reactor) by the ethylene / propylene ratio and the amount of vale.
    [33] By way of example and not limitation, hdr examples are described as described herein.
    [34] A first series of basic copolymers of propylene was prepared in a double reactor array where the matrix polymer was prepared in a first gas phase reactor and then transferred the contents of the first reactor to a second gas phase reactor. The ethylene content of the rubber phase (Ec) and the amount of the dispersed phase (Fc) Mr each ICP are presented in Table 1 below. Typical reaction conditions are used to produce these static copolymers. The melt flow index of the granules after the second reactor RV- each of these materials is about 1.4 g / 10 min. The powder granules are cracked so that the sand-beaten material has a final narrow-flow index of approximately 8 g / 10 minutes, by using Trigonox301 as a peroxide-containing viscosity reducing agent in a 30 mm co-rotating twin screw screw. A typical antioxidant package and nucleating agent Sodium benzoate 800 ppm was added to all examples during the viscosity reduction.
    [35] The pellet samples are injection molded according to ASTM D4101 with a 4-cavity family mold. The resulting cast dog bone is used RV bending and izod toughness feed. The resulting cast straight bar is used for heat resistance test (HDT) according to ASTM D648. The results of these tests are presented in Table 1.
    [36] As can be seen in the table, Examples 1 and 2 have better flexural modulus, ice toughness and heat resistance (HDT) than Comparative Examples 1 and 2 in most cases.
    [37] A second series of state copolymers of propylene are prepared as described above except that the powder granules are broken down to about 12 MF as shown in Table 2. Preparation of materials for testing and the tests themselves are performed as described above for Table 1. The results of these tests are presented in Table 2.
    [38] As can be seen in that table, Examples 3 and 4 have better flexural modulus, ice toughness and heat resistance (HDT) than Comparative Examples 3 and 4 in most cases.
    Table 2 Example 3 4 Cf. 3 Cf. 4 MF (g / 10 min), Rx 2 1,1.4 1.3 1.4 MF (g / 10 min), final 12.1 11.2 13.1 12 Ec, weight percent 52 56 46 Fc, weight percent 36 37 Bending, Kpsi 1% secant module 127 121 112 117 N. isod, foot-pound / inch (ftlb / in) @ 23 ° C 13,13,6 13,2 13,4 N. isod, foot-pound / inch (ftlb / in) @ 0 ° C 12.8 13.8 13.2 13.3 N. izod, foot-pound / inch (ftlb / in) @ -20 ° C 11.4 12.9 12 12.2 HDT, ° C 80 81 77 80 9
    权利要求:
    Claims (11)
    [1]
    A matrix comprising a homopolymer of polypropylene or a random copolymer of propylene / alpha-olefin comprising more than 50% by weight of units derived from propylene monomer, the homopolymer of polypropylene or the random copolymer of propylene / alpha-olefin having a large molecular weight to about 7 dal the matrix had a crystallinity of at least 50%,
    [2]
    A dispersed phase comprising a copolymer of ethylene-propylene comprising from 45 to 65% by weight of units derived from an ethylene monomer, the dispersed phase comprising from about 30 to 50% by weight of the impact copolymer of polypropylene. The impact copolymer of propylene according to claim 1, wherein the dispersed phase comprises from 30 to 40% by weight of the impact copolymer of polypropylene.
    [3]
    The impact propylene copolymer of claim 1 wherein the matrix comprises a polypropylene homopolymer.
    [4]
    The impact copolymer of propylene according to claim 1 ddr matrix had an MWD between 4 and 6.
    [5]
    An impact propylene copolymer according to claim 1, wherein the matrix comprises a random propylene / alpha-olefin copolymer comprising more than 90% by weight of units derived from propylene monomer.
    [6]
    An impact propylene copolymer according to claim 1 wherein the matrix comprises a random propylene / alpha-olefin copolymer in which the alpha-olefin is ethylene.
    [7]
    7. The impact copolymer of propylene according to claim 1 of the valley matrix had a crystallinity of more than 60%.
    [8]
    The impact copolymer of propylene according to claim 1, wherein the dispersed polymer comprises at least 50% by weight of ethylene. 10 537 777
    [9]
    A propylene impact copolymer according to claim 1 having a melt flow index of from 1 to 50 g / 10 min (230 ° C / 2.16 kg).
    [10]
    The impact copolymer of propylene according to claim 1 which has been subjected to viscosity reduction and whose viscosity reduction ratio is greater than or equal to 2.
    [11]
    The impact copolymer of propylene according to claim 10 in which the viscosity reduction ratio is greater than or equal to 4. 11
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US12/797,717|US8178623B2|2010-06-10|2010-06-10|High stiffness high impact propylene impact copolymers field of the invention|
    PCT/US2011/039247|WO2011156262A1|2010-06-10|2011-06-06|High stiffness high impact propylene impact copolymers|
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