JP2009530446A - Propylene / α-olefin block interpolymer - Google Patents

Abstract

Embodiments of the present invention provide a class of propylene / α-olefin block interpolymers. The propylene / α-olefin interpolymer is characterized by an average block index ABI that is greater than zero to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3. Preferably, the block index is from about 0.2 to about 1. In addition or alternatively, the block propylene / α-olefin interpolymer is characterized by having at least one fraction obtained by temperature programmed elution fractionation (“TREF”), wherein the fraction is about 0. A block index greater than 3 to about 1.0 and the propylene / α-olefin interpolymer has a molecular weight distribution M _w / M _n of greater than about 1.3.

Description

  The present invention relates to propylene / α-olefin block interpolymers and products made from those block interpolymers.

  Block copolymers include sequences of the same monomer units that are covalently linked to different types of sequences (“blocks”). These blocks can be connected in a variety of ways, such as AB and ABA triblock structures in diblocks, where A represents one block and B represents a different block. In multi-block copolymers, A and B can be connected in several different ways and can be repeated multiple times. In addition, different types of additional blocks can be included. The multi-block copolymer can be either a linear multi-block or a multi-block star polymer (all blocks bound to the same atom or the same chemical moiety).

  Block copolymers are created when two or more polymer molecules of different chemical composition are covalently bonded in an end-to-end manner. Although a wide variety of block copolymer structures are possible, most block copolymers contain a covalent bond of a hard plastic block that is substantially crystalline or glassy to an elastomeric block and is thermoplastic. Form an elastomer. Other block copolymers, such as rubber-rubber (elastomer-elastomer), glass-glass and glass-crystalline block copolymers are also possible and may have commercial significance.

  One method of making block copolymers is to produce a “living polymer”. Unlike the typical Ziegler-Natta polymerization method, the living polymerization method includes only an initiation step and a growth step and essentially lacks chain chain termination side reactions. This allows for the synthesis of predetermined and well-controlled structures that are desirable in block copolymers. Polymers created in “living” systems can have a narrow or very narrow molecular weight distribution and can be monodisperse (ie, essentially one molecular weight distribution). Living catalyst systems are characterized by an onset rate on the order of or above the growth rate and no growth stop or transfer reaction. In addition, these catalyst systems are characterized by the presence of a single type of active site. In order to produce high yield block copolymers in the polymerization process, the catalyst must exhibit a substantial degree of living properties.

  Butadiene-isoprene block copolymers have been synthesized by anionic polymerization using a continuous monomer addition technique. In continuous addition, a specific amount of one monomer is contacted with the catalyst. Once such a first monomer has reacted until it has substantially disappeared to form a first block, a specific amount of a second monomer or monomer species is introduced and reacted to form a second block. The process can be repeated with the same or other anionic polymerizable monomers. However, propylene and other α-olefins such as ethylene, butene, 1-octene and the like cannot be directly block polymerized by anionic techniques.

  There is therefore an unmet need for block copolymers based on propylene and α-olefins. There is also a need for a method for producing such block copolymers.

The foregoing needs are met by various aspects of the present invention. In one aspect, the present invention is a propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, having an average block index greater than zero to about 1.0 and a molecular weight greater than about 1.3. It relates to a propylene / α-olefin interpolymer characterized by a distribution M _w / M _n . In another aspect, the present invention is a propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, wherein the average block index is greater than 0 but less than about 0.4, and the molecular weight distribution M _w Relates to a propylene / α-olefin interpolymer having a / _Mn greater than about 1.3. Preferably, the interpolymer is a linear multiblock copolymer having at least 3 blocks. Furthermore, preferably the propylene content in the interpolymer is at least 50 mole percent.

In some embodiments, the average block index of the interpolymer is from about 0.1 to about 0.3, from about 0.4 to about 1.0, from about 0.3 to about 0.7, from about 0.6 to It is about 0.9, or in the range of about 0.5 to about 0.7. In other embodiments, the interpolymer has a density of less than about 0.90 g / cc, such as from about 0.85 g / cc to about 0.88 g / cc. In some embodiments, the α-olefin in the propylene / α-olefin interpolymer is styrene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene. 1,5-hexadiene or a combination thereof. In other embodiments, the molecular weight distribution M _w / M _n is greater than about 1.5 or greater than about 2.0. It can also range from about 2.0 to about 8 or from about 1.7 to about 3.5.

In yet another aspect, the present invention provides a propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, wherein at least one fraction obtained by temperature programmed elution fractionation (“TREF”) is obtained. A molecular weight distribution M _w / of which the fraction has a block index of greater than about 0.3 and up to about 1.0 and whose propylene / α-olefin interpolymer is greater than about 1.3. It relates to a propylene / α-olefin interpolymer having M _n . In yet another aspect, the invention is a propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, characterized in that it has at least one fraction obtained by TREF, the fraction A propylene / α-olefin interpolymer having a block index greater than about 0 and up to about 0.4, and the propylene / α-olefin interpolymer having a molecular weight distribution M _w / M _n greater than about 1.3 About. In some embodiments, the block index of the fraction is greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than about 0.7, greater than about 0.8, or It exceeds about 0.9.

  The interpolymer includes one or more hard segments and one or more soft segments. Preferably, the hard segment contains at least 98% propylene on a weight basis and the soft segment contains less than 95%, preferably less than 92% propylene on a weight basis. In some embodiments, the hard segment is present in an amount from about 5% to about 85% by weight of the interpolymer. In other embodiments, the interpolymer comprises at least 5 or at least 10 hard and soft segments that combine in a linear fashion to form a linear chain. Preferably, the hard and soft segments are randomly distributed along the chain. In some embodiments, neither the soft segment nor the hard segment includes a tip segment (which has a different chemical composition than the remaining segments).

  Methods for producing these interpolymers are also provided herein. Further aspects of the invention and features and characteristics of various embodiments of the invention will become apparent in the following description.

General Definition “Polymer” means a polymeric compound prepared by polymerization of monomers, whether of the same type or different types. The general term “polymer” encompasses the terms “homopolymer”, “copolymer”, “terpolymer” in addition to “interpolymer”.

  “Interpolymer” means a polymer prepared by the polymerization of at least two different types of monomers. The general term “interpolymer” is used in addition to the term “copolymer” (which is usually used to refer to a polymer prepared from two different monomers), which is usually three different The term is used to refer to polymers prepared from monomers of the type). In addition, it also includes polymers made by polymerizing four or more types of monomers.

  The term “propylene / α-olefin interpolymer” refers to a polymer in which propylene is the majority mole fraction of the total polymer. Preferably, propylene comprises at least 50 mole percent of the total polymer, more preferably at least 70 mole percent, at least 80 mole percent, or at least 90 mole percent, with the remainder of the total polymer including at least other comonomers. For propylene / ethylene copolymers, a preferred composition includes a propylene content greater than about 90 mole percent, with an ethylene content of about 10 mole percent or less. In some embodiments, the propylene / α-olefin interpolymer does not include what is produced in low yields or small amounts, or as a by-product of a chemical process. Although the propylene / α-olefin interpolymer can be blended with one or more polymers, the resulting propylene / α-olefin interpolymer is substantially pure and represents a major component of the polymerization process. Constitute.

  The term “crystalline”, when used, refers to a polymer or segment having a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. This term can be used interchangeably with the term “semicrystalline”. The term “amorphous” refers to a polymer that lacks a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

The term “multiblock copolymer” or “segmented copolymer” includes two or more chemically distinct regions or segments (also referred to as “blocks”), which are preferably linked in a linear fashion, That is, it refers to polymers that contain chemically distinct units that are end-to-end bonded to the polymerized propylene functional group rather than in a pendant or grafted manner. In preferred embodiments, these blocks comprise the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to the polymer of such composition, the type of stereoregularity or Degree (isotactic or syndiotactic), regio-regularity or regio-regularity, amount of branching, long chain or hyper-branching, homogeneity, or any other chemical or The physical properties are different. Multi-block copolymers are characterized by a unique distribution of both polydispersity indices (PDI or M _w / M _n ), block length distribution, and / or block number distribution due to the unique process of making the copolymer. More specifically, when produced in a continuous process, these polymers desirably have from about 1.7 to about 8, preferably from about 1.7 to about 3.5, more preferably from about 1.7 to about 1.7. It has a PDI of about 2.5, most preferably about 1.8 to about 2.5 or about 1.8 to about 2.1. When produced in a batch or semi-batch process, these polymers are about 1.0 to about 2.9, preferably about 1.3 to about 2.5, more preferably about 1.4 to about 2.0, Most preferably, it has a PDI of about 1.4 to about 1.8. Note that “block” and “segment” are used interchangeably herein.

In the following description, all numbers disclosed herein are approximate values, regardless of whether the word “about” or “approximately” is used in connection therewith. They can vary by 1 percent, 2 percent, 5 percent, or occasionally 10-20 percent. Whenever a numerical range with a lower limit R ^L and an upper limit R ^U is disclosed, any number falling within that range is explicitly disclosed. In particular, the following numbers within that range are explicitly disclosed. R = R ^L + k ^* (R ^U −R ^L ), where k is a variable that ranges from 1 percent to 100 percent in 1 percent increments, ie, k is 1 percent, 2 percent, 3 percent, 4 Percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent). Moreover, any numerical range defined by two R numbers as defined in the above is also disclosed explicitly.

Embodiments of the present invention provide a new class of propylene / α-olefin block interpolymers (hereinafter “polymers of the present invention”, “propylene / α-olefin interpolymers” or variations thereof). The propylene / α-olefin interpolymer comprises propylene and one or more copolymerizable α-olefin comonomers in polymerized form, and is composed of a plurality (ie Features two or more blocks or segments (block interpolymers), preferably multi-block copolymers. In some embodiments, the multi-block copolymer can be represented by the following formula:
(AB) _n .

  Where n is at least 1, preferably an integer greater than 1, for example 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more. belongs to. “A” represents a hard block or segment, and “B” represents a soft block or segment. Preferably, A and B are connected in a straight line format rather than a branched or star format. A “hard” segment refers to a block of polymerized units in which propylene is present in an amount greater than 95 weight percent, preferably greater than 98 weight percent. In other words, the comonomer content in the hard segment is less than 5 weight percent, preferably less than 2 weight percent. In some embodiments, all or substantially all of the hard segment comprises propylene. On the other hand, the “soft” segment refers to a block of polymerized units with a comonomer content greater than 5 weight percent, preferably greater than 8 weight percent, greater than 10 weight percent, or greater than 15 weight percent. In some embodiments, the comonomer content in the soft segment is greater than 20 weight percent, greater than 25 weight percent, greater than 30 weight percent, greater than 35 weight percent, greater than 40 weight percent, and greater than 45 weight percent. , Greater than 50 weight percent, or greater than 60 weight percent.

In some embodiments, the A and B blocks are randomly distributed along the polymer chain. In other words, these block copolymers do not have the following structure:
AAA--AA-BBB--BB

  In other embodiments, the block copolymer does not have a third type of block. In yet another embodiment, each of block A and block B has monomers or comonomers randomly distributed within the block. In other words, neither block A nor block B includes two or more segments (or sub-blocks) of different composition, eg, chip segments having a composition different from the rest of the block.

The propylene / α-olefin interpolymer is characterized by an average block index ABI of greater than zero to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3. The average block index ABI is a preparative TREF of 20 ° C. to 110 ° C. (ie, increased The weight average of each block index ("BI") of the polymer fraction obtained in the fractionation of polymer by elution fractionation method:
Where BI _i is the block index of the i-th fraction of the propylene / α-olefin interpolymer of the present invention obtained in preparative TREF and w _i is the weight percentage of the i-th fraction. Similarly, the square root of the second moment related to this average (hereinafter referred to as the second moment weight average block index) can be defined as follows.

Where N is defined as the number of fractions with BI _i greater than zero. For each polymer fraction, BI is defined by one of the following two equations, both of which yield the same BI value:
Where T _x is the ATREF (ie, analytical TREF) elution temperature of the i-th fraction (preferably expressed in Kelvin), and P _x is the propylene mole fraction of the i-th fraction, It can be measured by NMR or IR as described. P _AB is the propylene mole fraction of all propylene / α-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. T _A and P _A are the ATREF elution temperature and propylene mole fraction of pure “hard segments” (called interpolymer microcrystalline segments). As an approximation or for polymers where the "hard segment" composition is unknown, the T _A value and P _A values are set to those of isotactic polypropylene homopolymer catalyzed by a Ziegler-Natta catalyst.

T _AB has the same composition as the copolymers of the present invention, preferably the same stereoregularity and regio defects and molecular weight producing hard segments within the block copolymer (having propylene mole fraction P _AB ) , ATREF elution temperature of random copolymer. _TAB can be calculated from the molar fraction of propylene (measured by NMR) using the following equation:
Ln P _AB = α / T _AB + β

  Where α and β are determined by calibration using several well-characterized preparative TREF fractions of a well-characterized random propylene copolymer having a broad composition and / or a narrow composition. There are two constants that can be done. Ideally, these TREF fractions are prepared from random propylene copolymers produced with a catalyst that is substantially the same as or similar to the hard segment expected within the block copolymer. This is important to account for the slight temperature difference that results in propylene microcrystallinity due to defects from stereoregularity and regio insertion errors. If such random copolymers are not available, the TREF fraction from random copolymers produced by Ziegler-Natta catalysts known to produce highly isotactic polypropylene can be used. Note that α and β can vary from instrument to instrument. In addition, an appropriate calibration curve for the polymer composition of interest needs to be generated using the molecular weight range and comonomer type appropriate for the preparative TREF fraction and / or random copolymer used to create the calibration. There is a slight molecular weight effect. Such effects can be essentially ignored if calibration curves are obtained from similar molecular weight ranges.

T _XO is the ATREF temperature of a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight, and having a propylene mole fraction P _X. T _XO can be calculated from Ln P _X = α / T _XO + β and the measured molar fraction P _X. Conversely, P _XO is the propylene mole fraction of a random copolymer having the same composition (ie, the same comonomer type and content) and the same molecular weight, and having an ATREF temperature T _X , and Ln P _XO = α / T _X It can be calculated from the measured value T _X from + β.

  Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index ABI for the entire polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.4, or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.4 and up to about 1.0. Preferably, ABI should be in the range of about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, the ABI is from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6, It is in the range of about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, the ABI is from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, about It is in the range of 0.8 to about 1.0, or about 0.9 to about 1.0.

Another feature of the propylene / α-olefin interpolymers of the present invention includes at least one polymer fraction that the propylene / α-olefin interpolymers of the present invention can be obtained by preparative TREF, wherein the fraction is about Having a block index greater than 0.1 to about 1.0, and the polymer has a molecular weight distribution M _w / M _n greater than about 1.3. In some embodiments, the polymer fraction is greater than about 0.6 to about 1.0, greater than about 0.7 to about 1.0, greater than about 0.8 to about 1.0. Or a block index of greater than about 0.9 to about 1.0. In other embodiments, the polymer fraction is greater than about 0.1 to about 1.0, greater than about 0.2 to about 1.0, greater than about 0.3 to about 1.0. A block index of greater than about 0.4 to about 1.0, or greater than about 0.4 to about 1.0. In still other embodiments, the polymer fraction is greater than about 0.1 to about 0.5, greater than about 0.2 to about 0.5, greater than about 0.3 to about 0.5. Or a block index of about 0.4 to about 0.5. In yet another embodiment, the polymer fraction is greater than about 0.2 to about 0.9, greater than about 0.3 to about 0.8, greater than about 0.4 to about 0.7. Or a block index of about 0.5 to about 0.6.

  In addition to the average block index and the block index of the individual fractions, the propylene / α-olefin interpolymer is characterized by one or more of the properties described as follows.

In one embodiment, the propylene / alpha-olefin interpolymers used in embodiments of the present invention is from about 1.7 to about 3.5 M _w / M _n, at least one melting point T _m and wt% in degrees Celsius The numerical values of these variables correspond to the following relationship:
T _m > −2.909 (wt% α-olefin) +150.57, preferably
T _m ≧ −2.909 (wt% α-olefin) +145.57, more preferably
T _m ≧ -2.909 (wt% α-olefin) +141.57.

  Unlike traditional propylene / α-olefin random copolymers whose melting point decreases with decreasing density, the interpolymers of the present invention particularly have an α-olefin content of about 2 to about 15 wt%. Sometimes, it exhibits a melting point that is practically unrelated to the α-olefin content.

In yet another embodiment, the propylene / α-olefin interpolymer has a molecular fraction that elutes at 40 ° C. to 130 ° C. when fractionated using a temperature programmed elution fractionation method (“TREF”), wherein the fraction Is characterized by having a comonomer molar content higher than that of a comparative random propylene interpolymer eluting between the same temperatures, preferably at least 5 percent higher, more preferably at least 10 percent higher. Here, the comparative random propylene interpolymer contains the same comonomer and has a melt index, density and comonomer molar content (based on the total polymer) within 10 percent of that of the block interpolymer. Preferably, the _Mw / _Mn of the comparative interpolymer is also within 10 percent of that of the block interpolymer and / or the comparative interpolymer is within 10 weight percent of that of the block interpolymer. Has comonomer content.

In yet another aspect, the propylene / α-olefin interpolymer is characterized by a 300 percent strain and an elastic recovery rate Re expressed as a percent in one cycle as measured on a compression molded film of propylene / α-olefin interpolymer. And having a density d expressed in grams / cubic centimeter, the values of Re and d satisfy the following relationship when the propylene / α-olefin interpolymer is substantially free of cross-linked phase:
Re> 1481-1629 (d); preferably
Re> 1491-1629 (d); more preferably,
Re> 1501-1629 (d); even more preferably,
Re> 151 1-1629 (d).

  In some embodiments, the propylene / α-olefin interpolymer has a tensile strength greater than 10 MPa, preferably a tensile strength of ≧ 11 MPa, more preferably a tensile strength of ≧ 13 MPa and / or a crosshead separation of 11 cm / min. Having an elongation at break of at least 600 percent, more preferably 700 percent, very preferably at least 800 percent, and most preferably at least 900 percent.

  In other embodiments, the propylene / α-olefin interpolymer is (1) 1-50, preferably 1-20, more preferably 1-10, storage elastic ratio G ′ (25 ° C.) / G ′ (100 ° C.). And / or (2) having a 70 ° C. compression cure that decreases to less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent or less than 40 percent, 0 percent compression cure.

  In still other embodiments, the propylene / α-olefin interpolymer has a 70 ° C. compression cure of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent. Preferably, the 70 ° C. compression cure of these interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and can be as low as about 0 percent.

In some embodiments, the propylene / α-olefin interpolymer has a heat of fusion of less than 85 J / g and / or no more than 100 lb / ft ² (4800 Pa), preferably no more than 50 lb / ft ² (2400 Pa), especially 5 lb / It has a pellet blocking strength as low as ft ² (240 Pa) or lower and 0 lb / ft ² (0 Pa).

  In other embodiments, the propylene / α-olefin interpolymer, in polymerized form, comprises at least 50 mole percent propylene and is less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably 40-50 percent. Less than and has a 70 ° C. compression cure that drops to near zero percent.

  In some embodiments, the multi-block copolymer has a PDI that matches a Schultz-Flory distribution rather than a Poisson distribution. These copolymers are further characterized as having both a polydisperse block distribution and a polydisperse distribution of block size and having the most probable distribution of block lengths. Preferred multi-block copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, these copolymers comprise at least 5, 10 or 20 blocks or segments comprising end blocks.

In addition, the block interpolymers of the present invention have additional features or characteristics. In one aspect, preferably the interpolymer comprising propylene and one or more copolymerizable comonomers in polymerized form is a plurality of blocks or segments of two or more polymerized monomer units having different chemical or physical properties (blocked interpolymer) Most preferably, it features a multi-block copolymer, the block interpolymer having a molecular fraction that elutes between 40 ° C. and 130 ° C. when fractionated using TREF, the fraction eluting between the same temperatures It is characterized by having a comonomer molar content higher than that of the comparative random propylene interpolymer fraction, preferably at least 5 percent higher, more preferably at least 10 percent higher. Here, the comparative random propylene interpolymer comprises the same comonomer and has a melt index, density and comonomer molar content (based on the total polymer) within 10 percent of that of the blocked interpolymer. Preferably, the comparative interpolymer M _w / M _n is also within 10 percent of that of the blocked interpolymer and / or the comparative interpolymer is within 10 weight percent of that of the blocked interpolymer. Has comonomer content.

  Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance (“NMR”) analysis being preferred. Further, for polymers or polymer blends having a relatively broad TREF curve, first the polymer is fractionated using TREF into fractions each having an elution temperature range of 10 ° C. or lower. That is, each elution fraction has a collection temperature window of 10 ° C. or less. Using this technique, the block interpolymer has at least one fraction that has a higher comonomer molar content than the corresponding fraction of the comparative interpolymer.

In another embodiment, the polymer of the present invention preferably comprises a plurality of blocks of two or more polymerized monomer units comprising propylene and one or more copolymerizable comonomers in a polymerized form and having different chemical or physical properties. (I.e., at least two blocks) or segments (blocked interpolymers), most preferably olefin interpolymers characterized by multi-block copolymers, which elute at 40 <0> C to 130 <0> C (however, (Does not collect and / or isolate individual fractions) peaks (but not single molecular fractions), which are determined by infrared spectroscopy using full width at half maximum (FWHM) area calculations Same comonomer content as estimated when deployed Average comonomer mole content higher than that of the comparative random propylene interpolymer peak, preferably at least 5 percent higher, more preferably at least 10 percent higher, at the separation temperature and developed by full width at half maximum (FWHM) area calculations It is characterized by having a rate. Here, the comparative random propylene interpolymer has the same comonomer and has a melt index, density and comonomer molar content (based on the entire polymer) within 10 percent of that of the blocked interpolymer. . Preferably, the _Mw / _Mn of the comparative interpolymer is also within 10 percent of that of the blocked interpolymer and / or the comparative interpolymer is 10 weight percent of that of the blocked interpolymer. With a total comonomer content of within. The full width at half maximum (FWHM) calculation is based on the ratio [CH ₃ / CH ₂ ] of methyl to methylene response area from the ATREF infrared detector, where after identifying the tallest (highest) peak from the baseline Determine the FWHM area. For a distribution measured using an ATREF peak, FWHM area is defined as the area under the curve between T ₁ and T _2, T ₁ and T ₂ are, the left and right portions of the ATREF peak, the peak height Is the point that intersects the left and right parts of the ATREF curve, determined by dividing the line by 2 and then drawing a horizontal line on the baseline. A comonomer content calibration curve is generated using a random propylene / α-olefin copolymer and plotting the comonomer content from NMR against the FWHM area ratio of the TREF peak. For this infrared method, a calibration curve is generated for the same comonomer type of interest. The comonomer content of the TREF peak of the polymer of the invention can be determined by referring to this calibration curve using the FWHM methyl: methylene area ratio [CH ₃ / CH ₂ ] of the TREF peak.

  The comonomer content can be measured using any suitable technique, and techniques based on nuclear magnetic resonance (NMR) analysis are preferred. Using this technique, the blocked interpolymer has a higher comonomer molar content than the corresponding comparative interpolymer.

  Preferably, for propylene and ethylene interpolymers, the block interpolymer is greater than or equal to (−0.1236) T + 13.337, more preferably greater than or equal to (−0.1236) T + 14.837, 40-130 ° C. Has a comonomer content of the TREF fraction eluting at T, where T is the peak elution temperature value measured in ° C, for the TREF fraction to be compared.

In addition to the above aspects and properties described herein, the polymers of the present invention can be characterized by one or more additional features. In one embodiment, the polymer of the present invention preferably comprises a plurality of blocks of two or more polymerized monomer units having different chemical or physical properties, preferably comprising propylene and one or more copolymerizable comonomers in polymerized form. Segment (blocked interpolymer), most preferably an olefin interpolymer featuring a multi-block copolymer, the block interpolymer being a molecular fraction that elutes between 40 ° C. and 130 ° C. when fractionated using TREF increments And the fraction is higher than that of the comparative random propylene interpolymer fraction eluting between the same temperatures, preferably at least 5 percent higher, more preferably at least 10, 15, 20 or 25 percent higher Having a comonomer molar content The features. Here, the comparative random propylene interpolymer comprises the same comonomer, preferably it is the same comonomer, and the melt index, density and (with respect to the whole polymer) within 10 percent of the blocked interpolymer Has a comonomer molar content. Preferably, the comparable interpolymer M _w / M _n is also within 10 percent of that of the blocked interpolymer and / or the comparative interpolymer is within 10 weight percent of that of the blocked interpolymer. Has total comonomer content.

Preferably, the interpolymer is an interpolymer of propylene and at least one α-olefin, particularly an interpolymer having a total polymer density of about 0.855 to about 0.935 g / cm ³ , particularly about For polymers with greater than 1 mole percent comonomer, the blocked interpolymer is greater than or equal to (−0.1236) T + 13.337, more preferably greater than or equal to (−0.1236) T + 14.337, most preferably ( -0.1236) having a comonomer content of the TREF fraction eluting at 40-130 ° C, greater than or equal to the amount of T + 13.837, where T is the peak ATREF elution of the compared TREF fraction measured in ° C. It is a numerical value of temperature.

In yet another aspect, the polymer of the present invention preferably comprises a plurality of two or more polymerized monomer units having different chemical or physical properties, comprising propylene and one or more copolymerizable comonomers in polymerized form. Blocks or segments (blocked interpolymers), most preferably olefin interpolymers featuring multi-block copolymers, molecules that elute between 40 ° C. and 130 ° C. when fractionated using TREF increments All fractions having a fraction and having a comonomer content of at least about 6 mole percent have a melting point above about 100 ° C. For fractions having a comonomer content of about 3 mole percent to about 6 mole percent, all fractions have a DSC melting point of about 110 ° C. or higher. More preferably, the polymer fraction having at least 1 mole percent comonomer has a DSC melting point corresponding to the following equation:
Tm ≧ (−5.5926) (mole percent of comonomer in fraction) +135.90.

In yet another aspect, the polymer of the present invention preferably comprises a plurality of two or more polymerized monomer units having different chemical or physical properties, comprising propylene and one or more copolymerizable comonomers in polymerized form. Blocks or segments (blocked interpolymers), most preferably olefin interpolymers featuring multi-block copolymers, molecules that elute between 40 ° C. and 130 ° C. when fractionated using TREF increments All fractions having fractions and having an ATREF elution temperature of about 76 ° C. or higher have a melting enthalpy (fusion heat) corresponding to the following equation as determined by DSC:
Heat of fusion (J / gm) ≦ (3.1718) (ATREF elution temperature at ° C.)-136.58.

The block interpolymers of the present invention are molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, and all fractions having an ATREF elution temperature of 40 ° C. to less than about 76 ° C. It has a molecular fraction characterized by having a melting enthalpy (fusion heat) corresponding to the following equation as measured by DSC.
Heat of fusion (J / gm) ≦ (1.1312) (ATREF elution temperature at ° C.) + 22.97.

ATREF peak comonomer composition measurement with an infrared detector The comonomer composition of the TREF peak is measured using an IR4 infrared detector available from Polymer Char, Valencia, Spain (http://www.polymerchar.com/). Can do.

The “composition mode” of this detector comprises a measurement sensor (CH ₂ ) and a composition sensor (CH ₃ ), which are fixed narrowband infrared filters in the region of 2800 to 3000 cm ⁻¹ . The measurement sensor detects the methylene (CH ₂ ) carbon of the polymer, which is directly related to the polymer concentration in solution, whereas the composition sensor detects the methyl (CH ₃ ) group of the polymer. The numerical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the measured comonomer content of the polymer in solution and its response is calibrated with known propylene / alpha-olefin copolymer standards.

This detector, when used with an ATREF instrument, provides a signal response of both the concentration (CH ₂ ) and composition (CH ₃ ) of the polymer eluted during the TREF process. A polymer specific calibration can be created by measuring the area ratio of CH ₃ to CH ₂ for a polymer having a known comonomer concentration (preferably measured by NMR). The comonomer content of the ATREF peak of the polymer can be estimated by applying a reference calibration of the ratio of the area of individual CH ₃ and CH ₂ responses (ie, area ratio CH ₃ / CH ₂ to comonomer content).

The area of the peak can be calculated using full width at half maximum (FWHM) calculations after integrating the individual signal responses from the TREF chromatogram by applying an appropriate baseline. The full width at half maximum calculation is based on the ratio [CH ₃ / CH ₂ ] of methyl to methylene response area from the ATREF infrared detector, where after identifying the tallest (highest) peak from the baseline, the FWHM area To decide. The measured distribution using an ATREF peak, FWHM area is defined as the area under the curve between T ₁ and T _2, T ₁ and T ₂ are, until the left and right ATREF peak, by dividing the peak height by two Later, it is the point that intersects the left and right parts of the ATREF curve, determined by drawing a horizontal line on the baseline.

  The application of infrared spectroscopy to the measurement of polymer comonomer content in this ATREF infrared method is in principle similar to the GPC / FTIR system described in the following references. Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymer". Polymeric Materials Science and Engineering (1991), 65, 98 -100 .; and Deslauriers, PJ; Rohlfing, DC; Shieh, ET; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002) , 43, 59-170, both of which are incorporated herein by reference in their entirety.

  It should be noted that although the TREF fraction in the above description is obtained in 5 ° C increments, other temperature increments are possible. For example, the TREF fraction can be in 4 ° C increments, 3 ° C increments, 2 ° C increments or 1 ° C increments.

For copolymers of propylene and α-olefin, the polymer of the present invention preferably has (1) at least 1.3, more preferably at least 1.5, at least 1.7 or at least 2.0, most preferably at least 2.6, up to a maximum value of 5.0, more preferably up to a maximum of 3.5, in particular up to a maximum of 2.7; (2) a heat of fusion of 80 J / g or less; (3) A propylene content of at least 50 weight percent; (4) a glass transition temperature T _{g of} less than −5 ° C., more preferably less than −15 ° C. and / or (5) a unique T _m .

In addition, the polymers of the present invention, alone or in combination with any other properties disclosed herein, have a storage modulus G ′ of 400 kPa or higher at a temperature of log (G ′) of 100 ° C., preferably , 1.0 MPa or more. Furthermore, the polymers of the present invention have a relatively flat storage modulus as a function of temperature in the range of 0 to 100 ° C., which is characteristic of block copolymers and is characterized by olefin copolymers, in particular propylene and one or more _Nothing has been known about ethylene copolymers or C _4-8 aliphatic α-olefins. (In this context, the term “relatively flat” means that the decrease in log G ′ (Pascal notation) is 50-100 ° C., preferably 0-100 ° C., less than an order of magnitude).

The interpolymers of the present invention can be further characterized by a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa) in addition to a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 90 ° C. Alternatively, the interpolymers of the present invention can have a flexural modulus of at least 3 kpsi (20 MPa) in addition to a thermomechanical analysis penetration depth of 1 mm at a temperature of at least 104 ° C. They can be characterized as having an abrasion resistance (or volume loss) of less than 90 mm ³ .

In addition, these propylene / α-olefin interpolymers have a content of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably 0.01 to 500 g / 10 minutes, and particularly preferably 0.000. It can have a melt index I ₂ of 01-100 g / 10 min. In certain embodiments, these propylene / α-olefin interpolymers are 0.01-10 g / 10 min, 0.5-50 g / 10 min, 1-30 g / 10 min, 1-6 g / 10 min or 0.005%. It has a melt index I _{2 of 3} to 10 g / 10 min. In certain embodiments, the melt index of these propylene / α-olefin polymers is 1 g / 10 min, 3 g / 10 min, or 5 g / 10 min.

These polymers have a viscosity of 1,000 g / mol to 5,000,000 g / mol, preferably 1000 g / mol to 1,000,000, more preferably 10,000 g / mol to 500,000 g / mol, It may have 000 g / mol ～300,000G / mol molecular weight M _w. The density of the inventive polymers, 0.80~0.99g / cm ^3, preferably, the propylene-containing polymer may be ^{0.85g / cm 3 ~0.90g / cm 3} . In certain embodiments, the density of the propylene / α-olefin polymer ranges from 0.860 to 0.89 g / cm ³ or 0.865 to 0.885 g / cm ³ .

The process for producing these polymers is disclosed in the following patent applications. US Provisional Application No. 60 / 553,906, filed Mar. 17, 2004; US Provisional Application No. 60 / 662,937, filed March 17, 2005; US Provisional Application No. 60 / 662,937, filed March 17, 2005; No. 60 / 662,939; US Provisional Application No. 60/5662938 filed on Mar. 17, 2005; PCT Application No. PCT / US2005 / 008916 filed on Mar. 17, 2005; PCT Application No. PCT / US2005 / 008915; and PCT Application No. PCT / US2005 / 008917, filed March 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such method involves propylene and optionally one or more additional polymerizable monomers other than propylene under addition polymerization conditions.
(A) a first olefin polymerization catalyst having a high comonomer incorporation index;
(B) a second olefin polymerization catalyst having a comonomer uptake index of less than 90 percent, preferably less than 50 percent, most preferably less than 5 percent of the comonomer uptake index of catalyst (A), and (C) a chain shuttling agent. shuttling agent)
Contacting with a catalyst composition comprising a mixture or reaction product resulting from the combination.

  Typical catalysts and chain shuttling agents are as follows.

Catalyst (A1) is prepared according to the teachings of WO 03/40195, US Pat. Nos. 6,953,764 and 6,960,635 and WO 04/24740 [N- (2,6-di (1 -Methylethyl) phenyl) amide) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A2) is prepared according to the teachings of WO 03/40195, US Pat. Nos. 6,953,764 and 6,960,635 and WO 04/24740 [N- (2,6-di (1 -Methylethyl) phenyl) amide) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2-diyl) methane)] hafnium dimethyl.

The catalyst (A3) is bis [N, N ′ ″-(2,4,6-tri (methylphenyl) amido) ethylenediamine] hafnium dibenzyl.

Catalyst (A4) is bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) prepared substantially according to the teachings of US Pat. No. 6,897,276. Phenyl) -2-phenoxymethyl) cyclohexane-1,2-diylzirconium (IV) dibenzyl.

The catalyst (B1) is 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl. .

The catalyst (B2) is 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (2-methylcyclohexyl) imino) methyl) (2-oxoyl) zirconium dibenzyl. .

Catalyst (C1) is a (t-butylamido) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-η-indene prepared substantially according to the teachings of US Pat. No. 6,268,444. -1-yl) silane titanium dimethyl.

Catalyst (C2) is a (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a prepared substantially in accordance with the teachings of US Pat. No. 6,825,295. -Η-Inden-1-yl) silane titanium dimethyl.

Catalyst (C3) is a (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a prepared substantially according to the teachings of US Pat. No. 6,825,295. -Η-s-indacene-1-yl) silane titanium dimethyl.

Catalyst (D1) is bis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride available from Sigma-Aldrich.

  Shuttling agents The shuttling agents used include diethyl zinc, di (i-butyl) zinc, di (n-hexyl) zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis (dimethyl (t- Butyl) siloxane), i-butylaluminum bis (di (trimethylsilyl) amide), n-octylaluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butylaluminum, i-butylaluminum bis (di ( n-pentyl) amide), n-octylaluminum bis (2,6-di-t-butylphenoxide), n-octylaluminum di (ethyl (1-naphthyl) amide), ethylaluminum bis (t-butyldimethylsiloxide) ), Ethylaluminum di ( (Trimethylsilyl) amide), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptane) Amide), n-octylaluminum bis (dimethyl (t-butyl) siloxide, ethylzinc (2,6-diphenylphenoxide) and ethylzinc (t-butoxide).

Preferably, the process uses block copolymers, in particular multi-block copolymers, preferably 2 or more monomers, in particular ethylene and C _4-20 olefins or cycloolefins, using a plurality of catalysts that are not interchangeable. In particular, it takes the form of a continuous solution process to form linear _multiblock copolymers of C _4-20 α-olefins. That is, these catalysts are chemically separate. Under continuous solution polymerization conditions, the process is ideally suited for polymerization with a high monomer conversion of a mixture of monomers. Under these polymerization conditions, chain shuttling from the catalyst to the catalyst is advantageous compared to chain growth, and multiblock copolymers, especially linear multiblock copolymers, are formed with high efficiency.

  The interpolymers of the present invention can be distinguished from conventional random copolymers, physical blends of polymers, and block copolymers prepared by continuous monomer addition, flow catalyst, anionic or cationic living polymerization techniques. In particular, compared to the same monomer of equivalent crystallinity or modulus and random copolymer of monomer content, the interpolymer of the present invention has better (higher) heat resistance, higher measured by melting point It has a higher high temperature torsional storage modulus as determined by TMA penetration temperature, stronger high temperature tensile strength, and / or dynamic mechanical analysis. Compared to random copolymers containing the same monomers and monomer content, the interpolymers of the present invention have less compression cure, less stress relaxation, higher creep resistance, higher tear strength, and more, especially at elevated temperatures. High blocking resistance, faster cure due to higher crystallization (solidification) temperature, higher recovery rate (especially at higher temperatures), better wear resistance, stronger shrinkage and better oil and filler acceptability Have

  The interpolymers of the present invention also exhibit unique crystallization and branching distribution relationships. That is, the interpolymers of the present invention are particularly when compared to random copolymers containing the same monomers and monomer levels, or physical blends of polymers at equivalent overall densities, such as blends of high density polymers and low density copolymers. There is a relatively large difference between the maximum peak temperature as a function of heat of fusion measured using CRYSTAF and DSC. This unique feature of the inventive interpolymer is believed to be due to the unique distribution of the comonomer in the blocks within the polymer backbone. In particular, the interpolymers of the present invention can comprise alternating blocks of different comonomer content (including homopolymer blocks). The interpolymers of the present invention may also include a distribution that is a Schultz-Flory type distribution in the number and / or block size of polymer blocks that differ in density or comonomer content. In addition, the interpolymers of the present invention also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus and morphology. In a preferred embodiment, the microcrystalline hierarchy of these polymers is characteristic to distinguish them from random or block copolymers, even PDI values that are less than 1.7 or even less than 1.5 and even lower than 1.3. Small spherules and laminas are shown.

  Furthermore, the interpolymers of the present invention can be prepared using techniques that affect the degree or level of blockiness. That is, the amount of comonomer and the length of each polymer block or segment can be varied by controlling the polymerization temperature and other polymerization variables in addition to the ratio and type of catalyst and shuttling agent. The surprising advantage of this phenomenon is the discovery that as the degree of blocking increases, the resulting polymer's optical properties, tear strength and high temperature recovery properties improve. In particular, as the average number of blocks in the polymer increases, haze decreases while transparency, tear strength and high temperature recovery properties increase. By selecting a combination of shuttling agent and catalyst that has the desired chain transfer capability (high rate of shuttling at low levels of chain termination), other forms of polymer growth termination are effectively suppressed. Accordingly, the β-hydride removal observed in the polymerization of propylene / α-olefin comonomer mixtures according to embodiments of the present invention is minimal, if any, and the resulting crystalline block is highly or substantially complete. It is a straight chain and has little or no branching.

  Polymers with highly crystalline chain ends can be selectively prepared according to embodiments of the present invention. In elastomer applications, reducing the relative amount of polymer that stops at the amorphous block attenuates the intermolecular dilutive effect on the crystalline region. This result can be obtained by selecting chain shuttling agents and catalysts that respond appropriately to hydrogen or other chain terminators. Specifically, a catalyst that produces a highly crystalline polymer is more than a catalyst that is responsible for the production of less crystalline polymer segments (eg, due to more comonomer incorporation, regio-error or atactic polymer formation). When susceptible to chain chain termination (eg, due to the use of hydrogen), highly crystalline polymer segments preferentially occupy the polymer termination. Not only is the resulting terminating group crystalline, but upon termination, the catalytic sites that form a highly crystalline polymer can be reused to resume polymer formation. Thus, the initially formed polymer is another highly crystalline polymer segment. Thus, both ends of the resulting multiblock copolymer are preferentially highly crystalline.

The propylene α-olefin interpolymer used in embodiments of the present invention is preferably an interpolymer of propylene and at least one ethylene or C ₄ -C ₂₀ α-olefin. Particularly preferred are copolymers of propylene and ethylene or C ₄ -C ₂₀ α-olefins. These interpolymers may further comprise C ₄ -C ₁₈ diolefin and / or alkenylbenzene. Suitable unsaturated comonomers useful for polymerization with propylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes, and the like. Examples of such comonomers include ethylene or C ₄ -C ₂₀ α-olefins such as isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-heptene, Octene, 1-nonene, 1-decene and the like are included. 1-butene and 1-octene are particularly preferred. Other suitable monomers include styrene, halo or alkyl-substituted styrene, vinyl benzocyclobutane, 1,4-hexadiene, 1,7-octadiene and naphthenic materials (eg, cyclopentene, cyclohexene and cyclooctene).

Propylene / α-olefin interpolymer is the preferred polymer, but other propylene / olefin polymers can be used. Olefin as used herein refers to a family of unsaturated hydrocarbon-based compounds that contain at least one carbon-carbon double bond. Depending on the choice of catalyst, any olefin can be used in embodiments of the present invention. Preferably, suitable olefins are C ₄ -C ₂₀ aliphatic and aromatic compounds containing ethylene or vinylic unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene and in the 5 and 6 positions. C ₁ -C ₂₀ hydrocarbyl or cyclohydrocarbyl including norbornene substituted in the group is not limited thereto norbornene. In addition to mixtures of such olefins include mixtures of such olefins with C ₄ -C ₄₀ diolefin compounds.

Examples of olefin monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1 -Heptene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C ₄ -C ₄₀ diene (this includes 1,3-butadiene, 1,3-pentadiene, 1 , 4-Hexadiene, 1,5-hexadiene, 1,7-octadiene , 1,9-decadiene including but not limited to), contains other C ₄ -C ₄₀ alpha-olefins, and the like. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. Potentially any hydrocarbon containing vinyl groups can be used in embodiments of the present invention, but practical problems such as monomer availability, cost and convenient removal of unreacted monomer from the resulting polymer The ability to do so can become more problematic as the molecular weight of the monomer becomes excessive.

The polymerization methods described herein are well suited for the production of olefin polymers containing monovinylidene aromatic monomers, including styrene, o-methylstyrene, p-methylstyrene, t-butylstyrene and the like. In particular, interpolymers comprising propylene and styrene can be prepared by following the teachings herein. Optionally, copolymers with improved properties can be prepared, including propylene, styrene and C ₄ -C ₂₀ α-olefins, and optionally C ₄ -C ₂₀ dienes.

  Suitable non-conjugated diene monomers can be straight chain, branched chain or cyclic hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include, but are not limited to, linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9- Decadiene, branched acyclic diene such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and dihydromyricene and dihydroos Mixed isomers of ene, monocyclic alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and polycyclic alicycles Formula fused and bridged ring dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta 2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- ( 4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene. Of the dienes typically used in the preparation of EPDM, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5 -Methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be produced according to embodiments of the present invention are elastomeric interpolymers of ethylene, C ₄ -C ₂₀ α-olefins, particularly propylene, and optionally one or more diene monomers. is there. Preferred α-olefins for use in this embodiment of the invention are represented by the formula CH ₂ ═CHR ^* , where R ^* is a linear or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. . A particularly preferred α-olefin is propylene. Propylene-based polymers are commonly referred to in the art as EP or EPDM polymers. Suitable dienes for use in the preparation of such polymers, particularly multiblock EPDM type polymers, are conjugated or non-conjugated, linear or branched, cyclic or polycyclic dienes containing from 4 to 20 carbons. Is included. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene.

  The diene-containing polymer includes alternating segments or blocks containing higher or lower amounts of diene (including none) and α-olefin (including none) so that the diene and α- The total amount of olefin can be reduced. That is, the diene and alpha-olefin monomers are more effectively utilized because they are preferentially incorporated into certain types of blocks of the polymer rather than uniformly or randomly throughout the polymer, followed by polymer crosslinking. The density can be controlled better. Such crosslinkable elastomers and cured products have advantageous properties including stronger tensile strength and better elastic recovery.

In some embodiments, interpolymers of the present invention made with two types of catalysts that incorporate different amounts of comonomer have a weight ratio of blocks formed thereby of 95: 5 to 5:95. These elastomeric polymers desirably have a propylene content of 50 to 97 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 3 to 50 percent, based on the total weight of the polymer. Have. More preferably, the multiblock elastomeric polymers have a propylene content of 60-97 percent, a diene content of 0.1-10 percent, and an α-olefin of 3-40 percent, based on the total weight of the polymer. It has a content rate. Preferred polymers have a weight average molecular weight (M _w ) of 10,000 to about 2,500,000, preferably 20,000 to 500,000, more preferably 20,000 to 350,000, and less than 3.5. More preferred is a high molecular weight polymer having a polydispersity of less than 3.0 and a Mooney viscosity of 1 to 250 (ML (1 + 4) 125 ° C.). More preferably, such polymers have a propylene content of 65-75 percent, a diene content of 0-6 percent, and an α-olefin content of 20-35 percent.

  These propylene / α-olefin interpolymers can be functionalized by incorporating at least one functional group into the polymer structure. Exemplary functional groups include, for example, ethylenically unsaturated monofunctional and difunctional carboxylic acids, ethylenically unsaturated monofunctional and difunctional carboxylic acid anhydrides, salts thereof and esters thereof. obtain. Such functional groups can be grafted to a propylene / α-olefin interpolymer or copolymerized with propylene and any additional comonomers to produce an interpolymer of propylene, functional comonomers, and optionally other comonomers. Can be formed. Means for grafting functional groups to polypropylene are described, for example, in US Pat. Nos. 4,762,890, 4,927,888 and 4,950,541, the disclosures of these patents are Which are incorporated herein by reference in their entirety. One particularly useful functional group is maleic anhydride.

  The amount of functional groups present in the functional interpolymer can vary. Functional groups can typically be present in the copolymer-type functionalized interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, more preferably at least about 7 weight percent. Functional groups can typically be present in the copolymer-type functionalized interpolymer in an amount of less than about 40 weight percent, preferably less than about 30 weight percent, more preferably less than about 25 weight percent.

Further description of block index The random copolymer satisfies the following relationship: See PJ Flory, Trans. Faraday Soc., 51, 848 (1955), which is incorporated herein by reference in its entirety.

In Equation 1, the mole fraction P of the crystallizable monomer is related to the melting point T _m of the copolymer and the melting point T _m ⁰ of the pure crystallizable homopolymer. This equation is similar to the natural logarithmic relationship of the mole fraction of propylene as a function of inverse proportion of the ATREF elution temperature (° K).

  The relationship of propylene fraction to ATREF peak elution temperature and DSC melting point of various uniformly branched copolymers with similar stereoregularity and region defects is similar to the Flory equation. Similarly, the preparative TREF fraction of a random copolymer of almost all propylene and a random copolymer blend with similar stereoregularity and regio defects also rides on this line, except for small molecular weight effects.

  According to Flory, if the molar fraction P of propylene is equal to the conditional probability that one propylene unit is present before or after another propylene unit, the polymer is random. On the other hand, if the conditional probability that any two propylene units appear consecutively is greater than P, the copolymer is a block copolymer. If the conditional probability remains below P, an alternating copolymer results.

  The mole fraction of isotactic propylene in the random copolymer mainly determines the intrinsic distribution of the propylene segment, whose crystallization behavior is then governed by the minimum equilibrium crystal thickness at a given temperature. Thus, the copolymer melting temperature and TREF crystallization temperature of the block copolymers of the present invention are related to the magnitude of the deviation from a random relationship, such deviation being a random equivalent copolymer (or random) for a given TLER fraction. This is a useful method for quantifying how “blocky” is (relative to the equivalent TREF fraction). The term “blocked” refers to the extent to which a particular polymer fraction or polymer contains blocks of polymerized monomers or comonomers. There are two random equivalents, one corresponding to a constant temperature and one corresponding to a constant mole fraction of propylene. These form the sides of a right triangle.

The point (T _X , P _X ) represents the preparative TREF fraction, and the ATREF elution temperature T _X and NMR propylene mole fraction P _X are measured values. The propylene mole fraction P _{AB of the} entire polymer is also measured by NMR. For propylene copolymers, "hard segment" elution temperature and mole fraction (T _A, P _A) is either can be estimated, or otherwise (prepared by stereospecific Ziegler-Natta catalysts) isotactic propylene homopolymer Can be set to The T _AB value corresponds to the calculated random copolymer equivalent ATREF elution temperature based on the measured P _AB value. The corresponding random propylene mole fraction P _XO can also be calculated from the measured ATREF elution temperature T _X. The block index square is defined to be the ratio of the areas of the (P _X , T _X ) triangle and the (T _A , P _AB ) triangle. Since these right triangles are similar, the area ratio is also the square of the ratio of the distance from (T _A , P _AB ) and (T _X , P _X ) to the random line. In addition, the similarity of these right triangles means that any corresponding side length ratio can be used instead of area.

Most perfect block distribution point (T _A, P _AB) should be noted that corresponding to the whole polymer with a single eluting fraction, which is propylene such polymers in the "hard segments" This is because it preserves the segment distribution while still including all available octenes (perhaps in a run that is nearly identical to that produced by the soft segment catalyst). In most cases, the “soft segment” does not crystallize in ATREF (or preparative TREF).

Applications and End Uses The propylene / α-olefin block interpolymers of the present invention can be used to produce articles useful in a variety of conventional thermoplastic assembly processes, including casting, spraying, calendering. Or an object comprising at least one film layer, for example a monolayer film, or an object comprising at least one layer in a multilayer film, prepared by an extrusion coating method; molded article, for example blow molding, injection molding or rotational molding Articles; extrudates; fibers; and woven or non-woven fabrics. Thermoplastic compositions containing the polymers of the present invention include other natural or synthetic polymers, additives, reinforcing agents, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, foams. Blends with plasticizers and plasticizers are included. Particularly useful are multicomponent fibers, such as core / sheath fibers having an outer surface layer at least partially comprising one or more polymers according to embodiments of the present invention.

  Fibers that can be prepared from the polymers or blends of the present invention include staple fibers, tow, multicomponent, sheath / core, twisted and single fibers. Suitable fiber forming methods are disclosed in Spin Bonded, US Pat. Nos. 4,430,563, 4,663,220, 4,668,566 and 4,322,027. Melt spray technology, gel spun fibers as disclosed in US Pat. No. 4,413,110, woven and non-woven fabrics as disclosed in US Pat. No. 3,485,706, or other fibers such as polyester , Structures made from such fibers, including blends with nylon or cotton, thermoformed articles, extruded shapes, including profile extrusion and coextrusion, calendered articles and drawers, twisted or crimped yarns or Fiber is included. The novel polymers described herein are useful for forming molded articles, including wire and cable coating operations, as well as vacuum forming operations in sheet extrusion and the use of injection molding, blow molding or rotational molding methods. It is. Compositions comprising olefin polymers can also be used to form assembled articles, such as those described above, using conventional polyolefin processing techniques well known to those skilled in the art of polyolefin processing.

  Dispersions (both aqueous and non-aqueous) can also be formed using the polymers of the present invention or formulations containing them. Foamed foams containing the polymers of the present invention can also be formed as disclosed in PCT application No. PCT / US2004 / 027593, filed Aug. 25, 2004 and published as WO 2005/021622. These polymers can also be crosslinked by any known means such as the use of peroxides, electron beams, silanes, azides or other crosslinking techniques. These polymers can be chemically synthesized, for example, by the use of grafting (eg by using maleic anhydride (MAH), silane or other grafting agents), halogenation, amination, sulfonation or other chemical modifications. Can also be modified.

  Additives and adjuvants can be included in any formulation containing the polymer of the present invention. Suitable additives include fillers such as organic or inorganic particles (including clay, talc, titanium dioxide, zeolite, powdered metal), organic or inorganic fibers (carbon fiber, silicon nitride fiber, steel wire or mesh). Including), and nylon or polyester coatings, nano-sized particles, clays, etc .; tackifiers, oil extenders (including paraffinic or naphthenic oils); and other natural or synthetic polymers (others according to embodiments of the present invention) Including polymers).

  Suitable polymers for blending with the polymers according to embodiments of the present invention include thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers. Exemplary polymers for compounding include polypropylene (both impact modifying polypropylene, isotactic polypropylene, atactic polypropylene and random ethylene / propylene copolymers), multiple reactor PE (Ziegler) “In-reactor” blends of Natta PE and metallocene PE, such as US Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, Various types of polypropylene, including high pressure free radical LDPE, Ziegler Natta LLDPE, metallocene PE, including the products disclosed in US Pat. Nos. 5,869,575 and 6,448,341) (EVA), propylene / vinyl alcohol copoly Over, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS) as well as thermoplastic polyurethanes. Homogeneous polymers such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (eg, polymers available from The Dow Chemical Company and VISTAMAXX ™ available from ExxonMobil Chemical Company) under the trade name VERSIFY ™ It may be useful as a component in a blend containing the inventive polymer.

  Suitable end uses for the product include elastic films and fibers; soft goods such as toothbrush handles and furniture handles; gaskets and profiles; adhesives (including hot melt adhesives and pressure sensitive adhesives) Footwear (including soles and insoles); automotive interior parts and profiles; foam products (both open and closed cells); other thermoplastic polymers such as high density polypropylene, isotactic polypropylene or other olefin polymers Impact modifiers; coated fabrics; hoses; tubing; fillers; cap liners; flooring; and viscosity index modifiers for lubricants, also known as pour point modifiers.

  In some embodiments, a thermoplastic composition containing a thermoplastic matrix polymer, particularly an isotactic polypropylene and an elastomeric multi-block copolymer of propylene and copolymerizable comonomers according to embodiments of the present invention, is uniquely hard. It is possible to form core-shell type particles having crystalline or semi-crystalline blocks in the form of a core surrounded by a soft or elastomeric block that forms a “shell” around the occlusive domain of the hard polymer. These particles are formed and dispersed within the matrix polymer due to the forces experienced during melt mixing or compounding. This highly desirable form is a multiblock that allows compatible polymer regions, for example, the higher comonomer content elastomeric regions of the matrix and multiblock copolymers to self-assemble in the molten state by thermodynamic forces. It is thought to be caused by the unique physical properties of the copolymer. It is believed that the shear force during mixing produces a separation region of the matrix polymer that is surrounded by the elastomer. Upon solidification, these regions become occluded elastomer particles encased in a polymer matrix.

  Particularly desirable blends are thermoplastic polyolefin blends (TPO), thermoplastic elastomer blends (TPE), thermoplastic vulcanizates (TPV) and styrene polymer blends. TPE and TPV blends can be combined with a multi-block polymer of the present invention containing functionalized or unsaturated derivatives thereof, any rubber containing a conventional block copolymer, in particular an SBS block copolymer, and optionally a crosslinking or vulcanizing agent. It can be prepared by combining. TPO blends are generally prepared by blending the multi-block copolymers of the present invention with a polyolefin and optionally a crosslinking or vulcanizing agent. Said blends can be used in the formation of the molding substance and optionally in the crosslinking of the resulting molded article. A similar procedure using different components is conventionally disclosed in US Pat. No. 6,797,779.

  Conventional block copolymers suitable for this application desirably have a Mooney viscosity (ML1 + 4 @ 100 ° C.) in the range of 10 to 135, more preferably 25 to 100, and most preferably 30 to 80. Suitable polyolefins include in particular linear or low density polyethylene, polypropylene (including their atactic, isotactic, syndiotactic and impact modifiers) and poly (4-methyl-1-pentene). It is. Suitable styrene polymers include polystyrene, rubber modified polystyrene (HIPS), styrene / acrylonitrile copolymer (SAN), rubber modified SAN (ABS or AES) and styrene maleic anhydride copolymer.

  These blends can be prepared by mixing or kneading each component at a temperature near or above the melting point of one or both of the components. For most multiblock copolymers, this temperature can be greater than 130 ° C, most commonly greater than 145 ° C, and most preferably greater than 150 ° C. Typical polymer mixing or kneading equipment can be used that reaches the desired temperature and is capable of melt plasticizing the mixture. These include mills, kneaders, extruders (both single screw and twin screw), Banbury mixers, calendars and the like. The order and method of mixing can depend on the final composition. A combination of a Banbury batch mixer and a continuous mixer, such as a Banbury mixer, then a mill mixer, and then an extruder can also be used. Typically, a TPE or TPV composition has a higher input of crosslinkable polymer (typically a conventional block copolymer containing unsaturation) compared to a TPO composition. Generally, for TPE and TPV compositions, the weight ratio of block copolymer to multi-block copolymer is about 90:10 to 10:90, more preferably 80:20 to 20:80, and most preferably 75:25 to 25-25. : 50. For TPO applications, the weight ratio of multiblock copolymer to polyolefin can be from about 49:51 to 5:95, more preferably from 35:65 to about 10:90. For modified styrene polymer applications, the weight ratio of multiblock copolymer to polyolefin can also be from about 49:51 to about 5:95, more preferably from 35:65 to about 10:90. These ratios can be changed by changing the viscosity ratio of the various components. There are a number of documents that describe techniques for changing phase continuity by changing the viscosity ratios of the components of the blend and can be consulted by those skilled in the art if necessary.

  The formulation composition can include a processing oil, a plasticizer, and a processing aid. Rubber treated oils having a specific ASTM name and paraffinic, naphthenic or aromatic treated oils are all suitable for use. Generally, 0 to 150 parts, more preferably 0 to 100 parts, and most preferably 0 to 50 parts of oil are used per 100 parts of the total polymer. Larger amounts of oil may have a tendency to improve processing of the resulting product at the expense of some physical properties. Further processing aids include conventional waxes, fatty acid salts such as calcium or zinc stearate, (poly) alcohols containing glycols, (poly) alcohol ethers containing glycol ethers, (poly) glycol esters (poly). ) Esters as well as their metal salts, in particular group 1 or 2 metal or zinc salt derivatives.

  Non-hydrogenated rubbers, such as those containing polymerized forms of butadiene or isoprene (including diene rubbers), including block copolymers, are less resistant to UV, ozone and oxidation than most or highly saturated rubbers It is known. In applications such as tires made from compositions containing high concentrations of diene rubbers, it is known to improve rubber stability by incorporating carbon black with anti-ozone additives and antioxidants. Multiblock copolymers according to the invention with extremely low levels of unsaturation adhere to articles formed from protective surface layers (coated, coextruded or laminated) or conventional diene elastomer modified polymer compositions Special applications are found as weathering films to be made.

In conventional TPO, TPV and TPE applications, carbon black is the select additive for UV absorption and stabilization properties. Representative examples of carbon black include ASTM N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550. , N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have an average pore volume in the range of Iodine and 10~150cm ³ / 100g ranging from 9 to 145 g / kg. In general, carbon black with a smaller particle size is used to the extent permitted by cost considerations. For many such applications, the multi-block copolymers and their blends of the present invention require little or no carbon black, thereby providing considerable design freedom with or without alternative pigments. Is possible. One possibility is multi-hued tires or tires that match the color of the vehicle.

  Compositions comprising thermoplastic blends according to embodiments of the present invention can also include anti-ozonating materials and antioxidants known to rubber chemists having ordinary skill. The anti-ozonating material may be a physical protective agent, for example, a waxy material that reaches the surface and protects it from oxygen or ozone, or may be a chemical protective agent that reacts with oxygen or ozone. . Suitable chemical protectants include butylated reaction products of styrenated phenol, butylated octylated phenol, butylated di (dimethylbenzyl) phenol, p-phenylenediamine, p-cresol and dicyclopentadiene (DCPD), Polyphenolic antioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants, thioester antioxidants and blends thereof are included. Some representative trade names for such products are Wingstay ™ S antioxidant, Polystay ™ 100 antioxidant, Polystay ™ 100AZ antioxidant, Polystay ™ 200 antioxidant. , Wingstay ™ L antioxidant, Wingstay ™ LHLS antioxidant, Wingstay ™ K antioxidant, Wingstay ™ 29 antioxidant, Wingstay ™ SN-1 antioxidant and Irganox (Trademark) Antioxidant. For some applications, the antioxidants and antiozonants used are preferably non-staining and non-migrating.

  Hindered amine light stabilizers (HALS) and UV absorbers can also be used to provide additional stability to UV radiation. Suitable examples include Tinuvin ™ 123, Tinuvin ™ 144, Tinuvin ™ 622, Tinuvin ™ 765, Tinuvin ™ 770 and Tinuvin ™ 780 available from Ciba Specialty Chemicals and the United States. Chemisorb ™ T944 available from Cytex Plastics, Houston, Texas. In order to achieve excellent surface quality, a Lewis acid can be additionally included with the HALS compound, as disclosed in US Pat. No. 6,051,681.

  In some compositions, antioxidants, anti-ozonants, carbon black, UV absorbers and / or light stabilizers are predispersed to form a masterbatch and then from them to form a polymer blend. Further mixing processes can be used.

  Suitable crosslinking agents (also called curing or vulcanizing agents) for use herein include sulfur-based, peroxide-based or phenolic compounds. Examples of such materials are U.S. Pat. Nos. 3,758,643, 3,806,558, 5,051,478, 4,104,210, 4,130,535, No. 4,202,801, No. 4,271,049, No. 4,340,684, No. 4,250,273, No. 4,927,882, No. 4,311,628 and No. 5,248 , 729, and the like.

  When sulfur-based curing agents are used, accelerators and curing activators can also be used. Accelerators are used to control the time and / or temperature required for dynamic vulcanization and to improve the properties of the resulting crosslinked article. In one embodiment, a single accelerator or primary accelerator is used. The primary accelerator can be used in a total amount ranging from about 0.5 to about 4, preferably from about 0.8 to about 1.5 phr, based on the total composition weight. In another embodiment, a combination of primary and secondary accelerators can be used to activate and improve the properties of the cured article, with a lower amount of secondary accelerator, eg, about 0.05 to about 3 phr. Used in The combination of accelerators generally produces an article with somewhat better properties than those produced by the use of a single accelerator. In addition, delayed action accelerators can be used that are not affected by normal processing temperatures but still produce satisfactory cure at normal vulcanization temperatures. A vulcanization inhibitor can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is sulfenamide. When a secondary accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound. Certain processing aids and cure activators such as stearic acid and ZnO can also be used. When peroxide based curing agents are used, co-activators or co-agents can be used in combination with them. Suitable co-crosslinking agents include, among others, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC). The use of peroxide crosslinkers and optional co-crosslinkers used for partial or complete dynamic vulcanization is known in the art, for example the publication “Peroxide Vulcanization of Elastomers”, Vol. 74, No 3 , July-August 2001.

  When a multi-block copolymer containing composition is at least partially crosslinked, the degree of crosslinking can be measured by dissolving the composition in a solvent for a specified time and calculating the percent gel or non-extractable component. . Gel percent usually increases with increasing level of crosslinking. In cured articles according to embodiments of the present invention, the percent gel content is desirably in the range of 5 to 100 percent.

  In addition to the multi-block copolymers according to embodiments of the present invention, their blends have improved processability, although thought to be due to a lower melt viscosity compared to prior art compositions. Thus, the composition or blend exhibits an improved surface appearance, particularly when formed into a molded or extruded article. At the same time, the compositions of the present invention and their blends uniquely have improved melt strength properties, thereby making the multi-block copolymers and their blends of the present invention, especially TPO blends, currently poor in melt strength. It can be usefully used in suitable foam and thermoforming applications.

  Thermoplastic compositions according to embodiments of the present invention include organic or inorganic fillers or other additives such as starch, talc, calcium carbonate, glass fibers, polymer fibers (including nylon, rayon, cotton, polyester and polyaramid) , Metal fibers, flakes or particles, expandable layered silicates, phosphates or carbonates, eg, clays, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon whiskers, carbon fibers, nanotubes and nano It may also contain particles, wollastonite, graphite, zeolites and ceramics such as silicon carbide, silicon nitride or titania. Silane-based or other coupling agents can also be used for better filler bonding.

  The thermoplastic composition according to an embodiment of the present invention comprises the blend and is obtained by conventional molding techniques such as injection molding, extrusion molding, thermoforming, slush molding, overmolding, insert molding, blow molding and other techniques. Can be processed. Films including multilayer films can be produced by casting or tentering methods, including spray film methods.

  In addition to the above, these block propylene / α-olefin interpolymers can also be used in the manner described in the following US Provisional Application, the disclosures of this application and their pending, divisional and partially pending applications are incorporated by reference. All of which are incorporated herein. “Fibers Made from Copolymers of Propylene / α-Olefins”, US Application No. 60 / 717,863, filed September 16, 2005.

Test method ATREF
Analytical temperature-programmed elution fractionation (ATREF) analysis is described in US Pat. No. 4,798,081 and Wilde, L .; Ryle, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982), which are incorporated herein by reference in their entirety. By dissolving the composition to be analyzed in trichlorobenzene and gradually lowering the temperature to 20 ° C. at a cooling rate of 0.1 ° C./min in a column containing an inert support (stainless steel shot). Crystallize. The column is equipped with an infrared detector. Subsequently, an ATREF chromatogram curve is generated by eluting the crystallized polymer sample from the column by gradually increasing the temperature of the eluting solvent (trichlorobenzene) from 20 ° C. to 120 ° C. at a rate of 1.5 ° C./min. .

Polymer fractionation by TREF The large-scale TREF fraction is obtained by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring at 160 ° C. for 4 hours. The polymer solution was 30-40 mesh (600-425 μm) spherical industrial grade glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801) and stainless steel 0.028 with 15 psig (100 kPa) nitrogen. "(0.7 mm) diameter cut wire shot (available from Pellets. Inc., 63 Industrial Drive, North Tonawanda, NY, 14120) 3" x 4 "(7 (6 cm × 12 cm) is pushed into a steel column, which is immersed in a thermally controlled oil jacket, initially set at 160 ° C. The column is first ballistically cooled to 125 ° C. and then each time Min 0.04 Slowly cool to 20 ° C. and hold for 1 hour Fresh TCB is introduced at approximately 65 ml / min while the temperature is increased at 0.167 ° C. per minute.

  Collect approximately 2000 ml from the eluate from the preparative TREF column in a 16-station heated fraction collector. In each fraction, the polymer is concentrated using a rotary evaporator until approximately 50-100 ml of polymer solution remains. Allow the concentrated solution to stand overnight, then add excess methanol, filter and rinse (about 300-500 ml of methanol, including final rinse). This filtration step is performed using a 5.0 μm polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat # Z50WP04750) at a three point vacuum assisted filtration station. The filtered fraction is dried in a vacuum oven at 60 ° C. overnight and weighed on an analytical balance prior to further testing. More information on this technology can be found in Wilde, L .; Ryle, TR; Knobeloch, DC; Peat, IR; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982). Be taught.

DSC Standard Method Differential scanning calorimetry results are determined using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge stream of 50 ml / min is used. The sample is compressed into a thin film, melted in a press at about 190 ° C., and then air-cooled to room temperature (25 ° C.). Next, 3-10 mg of material is cut into 6 mm diameter discs, accurately weighed, placed in a lightweight aluminum pan (about 50 mg), and then crimped closed. The thermal behavior of the sample is examined with the following temperature profile. The sample is rapidly heated to 230 ° C. and held isothermal for 3 minutes to remove any previous thermal history. The sample is then cooled to -90 ° C at a cooling rate of 10 ° C / min and held at -90 ° C for 3 minutes. The sample is then heated to 230 ° C. at a heating rate of 10 ° C./min. Record the cooling and second heating curve.

  The DSC melting peak is measured as the maximum heat flow rate (W / g) relative to a linear baseline drawn between the beginning and end of melting. The heat of fusion is measured as the area under the melting curve between the beginning and end of melting using a linear baseline. For polypropylene homopolymers and copolymers, the beginning of melting is typically observed at 0-40 ° C. The resulting enthalpy curve is analyzed for peak melting temperature, onset, and peak crystallization temperature, heat of fusion and heat of crystallization, and any other DSC analysis value of interest.

  DSC calibration is performed as follows. First, a baseline is obtained by running the DSC from −90 ° C. without any sample in the aluminum DSC pan. Next, 7 milligrams of fresh indium sample was heated to 180 ° C. and cooled to 140 ° C. at a cooling rate of 10 ° C./min, then held isothermally at 140 ° C. for 1 minute, then 10 ° C. per minute Analysis is carried out by heating from 140 ° C. to 180 ° C. at a heating rate of Check the heat of fusion and the onset of melting of the indium sample by determining it from 156.6 ° C. to 0.5 ° C. for the onset of melting and 28.71 J / g to 0.5 J / g for the heat of fusion. . The deionized water is then analyzed by cooling a small drop of fresh sample in the DSC pan from 25 ° C. to −30 ° C. at a cooling rate of 10 ° C. per minute. The sample is isothermally held at −30 ° C. for 2 minutes and heated to 30 ° C. at a heating rate of 10 ° C. per minute. Determine and check the start of melting within 0.5 ° C. to 0 ° C.

The GPC method gel permeation chromatography system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments operate at 140 ° C. Three Polymer Laboratories 10-micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 ml / min.

Molecular weight determination is estimated by using 10 narrow molecular weight distribution polystyrene standards (from Polymer Laboratories, EasiCal PS1 in the range of 580-7,500,000 g / mol) in conjunction with their elution volumes. The equivalent polypropylene molecular weight is (Th.G. Scholte, NLJ Meijerink, HM Schoffeieers, and AMG Brands, J. Appl. Polym. Sci., 29. 3763-3782 (1984), which is incorporated herein by reference. For polypropylene) and for polystyrene (described by EP Otocka, RJ Roe, NY Hellman, PM Muglia, Macromolecules, 4, 507 (1971), which is incorporated herein by reference). The appropriate Mark-Houwink coefficient for the Mark-Houwink equation:
{Η} = KM ^a
In which K _{pp =} 1.90E-04, a _{pp =} 0.725 and K _{ps =} 1.26E-04, a _{ps =} 0.702.

  Polypropylene equivalent molecular weight is calculated using Viscotek TriSEC software version 3.0.

¹³ C NMR
The copolymers of the present invention typically have a substantially isotactic propylene sequence. “Substantially isotactic propylene sequences” and similar terms indicate that the sequences are greater than about 0.85, preferably greater than about 0.90, more preferably greater than about 0.92, as measured by ¹³ C NMR. , Most preferably having an isotactic triad (mm) greater than about 0.93. Isotactic triads are well known in the art and are described, for example, in USP 5,504,172 and WO 00/01745, which are in terms of triad units in copolymer molecular chains determined by ¹³ C NMR spectra. Refers to isotactic sequence. The NMR spectrum is determined as follows.

¹³ C NMR spectroscopy is one of several techniques known in the art for measuring comonomer efforts on polymers. An example of this technique is described in Randall (Journal of Macromolecular Science, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3), 201-317 (1989)) for the determination of comonomer content of ethylene / α-olefin copolymers. . The basic procedure for determining the comonomer content of an olefin interpolymer is to obtain a ¹³ C NMR spectrum under conditions where the intensity of peaks corresponding to different carbons in the sample is directly proportional to the total number of contributing nuclei in the sample. including. Methods to ensure this proportionality are known in the art and include allocation of time sufficient for post-pulse relaxation, the use of gated decoupling techniques, relaxation agents, and the like. In practice, the relative intensity of a peak or group of peaks is obtained from its computer-generated integral. After obtaining the spectrum and integrating the peaks, the peaks associated with the comonomer are assigned. This assignment can be made by reference to known spectra or literature, or by synthesis and analysis of model compounds, or by the use of isotopically labeled comonomers. Comonomer mole% can be determined by the ratio of the integral to the integral corresponding to the number of moles of all monomers in the interpolymer, corresponding to the number of moles of comonomer, as described, for example, in Randall.

Data is collected using a Varian UNITY Plus 400 MHz NMR spectrometer or JEOL Eclipse 400 NMR spectrometer, corresponding to a ¹³ C resonance frequency of 100.4 or 100.5 MHz, respectively. Acquisition parameters are selected to ensure quantitative ¹³ C data acquisition in the presence of a relaxation agent. Data was heated to 130 ° C using a gated 1H decoupling, 4000 transients per data file, 6 second pulse repetition delay, 24,200 Hz spectral width and 32K data point file size. While getting. Samples are added to 0.4 g of sample in a 10 mm NMR tube, approximately 3 mL of a 50/50 mixture of 0.025 M tetrachloroethane-d2 / orthodichlorobenzene (relaxation agent) in chromium acetylacetonate. Prepare by. The head space of the tube is purged of oxygen by replacing with pure nitrogen. The sample is dissolved and homogenized by heating the tube and its contents to 150 ° C. with periodic reflux initiated by a heat gun and periodic vortexing of the tube and contents.

  After data collection, the chemical shift is internally referenced to 21.90 ppm mmmm pentad. Isotacticity at the triad level (mm) is a methyl integral representing mm triad (22.5-21.28 ppm), mr triad (21.28-20.40 ppm) and rr triad (20.67-19.4 ppm). Determine from. The percentage of mm stereoregularity is determined by dividing the strength of the mm triad by the sum of mm, mr and rr triads. For propylene-ethylene copolymers made with catalyst systems, eg, nonmetallocene metal-centered heteroaryl complex catalysts (described above), the mr region is corrected for ethylene and regio errors by subtracting contributions from PPQ and PPE. In these propylene-ethylene copolymers, the rr region is corrected for ethylene and regio errors by subtracting the contribution from PQE and EPE. For copolymers containing other monomers that produce peaks in the mm, mr, and rr regions, once the peaks are identified, the integration of these regions is similarly corrected by subtracting the interference peaks using standard NMR techniques. . This can be accomplished, for example, by analyzing a series of copolymers of varying levels of monomer incorporation, by literature assignment, by isotope labeling, or by other means known in the art.

For copolymers prepared using nonmetallocene metal-centered heteroaryl complex catalysts, such as those described in US 2003/0204017, ¹³ C NMR corresponding to regio-errors of about 14.6 and about 15.7 ppm The peak is believed to be the result of a stereoselective 2,1-insertion error of the propylene unit into the growing polymer chain. In general, for a given comonomer content, a higher level of regioerror leads to a lowering of the melting point and modulus of the polymer, whereas a lower level leads to a higher melting point and higher modulus of the polymer.

Matrix Calculations For propylene / ethylene copolymers, the following procedure can be used to determine comonomer composition and sequence distribution. The integration area is determined from the ¹³ C NMR spectrum and input into the matrix calculation to determine the molar fraction of each triad sequence. The matrix arrangement is then used with their integrals to obtain the mole fraction of each triad. The matrix calculation was modified to include additional peaks and sequences of 2,1 regio errors, the method of Randall (Journal of Macromolecular Chemistry and Physics, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3), 201-317, 1989). Is a linear least square implementation. Table B shows the integration regions and triad assignments used in the assignment matrix. The number associated with each carbon indicates the region of the spectrum where it resonates.

Mathematically, the matrix method is a vector expression s = fM, where M is a configuration matrix, s is a spectral row vector, and f is a mole fraction composition vector. For a good implementation of the matrix method, the resulting equation is determined or over determined (equal to a variable or more independent), and the numerator required to compute the desired structural information It is required that M, f, and s be defined to include information. The first step in the matrix method is to determine the elements in the composition vector f. The elements of this vector must be molecular parameters selected to provide structural information about the system being studied. For copolymers, a reasonable set of parameters is an arbitrary odd n-ad distribution. Usually, the peaks from individual triads are reasonably well resolved and easy to assign, so the triad distribution is most often used in this composition vector f. The triads of E / P copolymers are EEE, EEP, PEE, PEP, PPP, PPE, EPP and EPE. For reasonably sized molecular weight (> = 10,000 g / mol) polymer chains, ¹³ C NMR experiments cannot distinguish EEP from PEE or PPE from EPP. Moreover, because all Markovian E / P copolymers have PEE and EPP mole fractions equal to each other, an quality restriction was also chosen for implementation. The same process was performed for PPE and EPP. The above two identity restrictions reduce the eight triads to six independent variables. For reasons of clarity, the composition vector f is still represented by all eight triads. Identity restrictions are implemented as internal restrictions when solving the matrix. The second step in the matrix method is to define the spectral vector s. Usually the elements of this vector are well defined integration regions in the spectrum. In order to guarantee the determined system, the number of integrals needs to be as large as the number of independent variables. The third stage is to determine the arrangement matrix M. This matrix is constructed by finding the carbon (column) contribution of the central monomer unit in each triad for each integration region (row). When determining which carbons belong to the central unit, it is necessary to be consistent with respect to the direction of polymer growth. A useful property of this configuration matrix is that the sum of each row must be equal to the number of carbons in the triad's central unit that contributes to that row. This identity can be easily checked and therefore some common data entry errors can be prevented.

  After building the placement matrix, it is necessary to perform a redundancy check. In other words, the number of linearly independent columns needs to be greater than or equal to the number of independent variables in the product vector. If the matrix fails the redundancy test, it is necessary to return to the second stage and redefine the placement matrix by subdividing the integration region until the redundancy check is passed.

  In general, when the number of additional restrictions or constraints in addition to the number of columns is greater than the number of rows in matrix M, the system is overdetermined. The greater this difference, the more the system is determined. The more the system is determined, the more the matrix method can correct or identify inconsistent data that may result from integration of low signal-to-noise (S / N) ratio data or partial saturation of some resonances. .

The final step is to solve the matrix. This is easily done by using the Solver function in Microsoft Excel. Solver operates by first estimating the solution vector (molar ratio between different triads) and repeatedly estimating so that the sum of the difference between the calculated product vector and the input product vector is minimized. Solver also asks for explicit input of restrictions or constraints.

  The 1,2-inserted propylene composition is calculated by summing all stereoregular propylene center triad sequence mole fractions. The 2,1-inserted propylene composition (Q) is calculated by summing all Q-centered triad sequence mole fractions. The mole percent is calculated by multiplying the mole fraction by 100. The C2 composition is determined by subtracting the P and Q molar percentage values from 100.

Example 2
Metallocene Catalyst This example shows the calculation of the composition value of a propylene-ethylene copolymer produced using a metallocene catalyst synthesized according to Example 15 of USP 5,616,664. The propylene-ethylene copolymer is prepared according to Example 1 of US Patent Application 2003/0204017. The propylene-ethylene copolymer is analyzed as follows. Data is collected using a Varian UNITY Plus 400 MHz NMR spectrometer corresponding to a ¹³ C resonance frequency of 100.4 MHz. Acquisition parameters are selected to ensure quantitative ¹³ C data acquisition in the presence of a relaxation agent. Data is acquired while heating the probe head to 130 ° C. using gated 1H decoupling, 4000 transients per data file, 7 second pulse repetition delay, 24,200 Hz spectral width and 32K data point file size. . Samples are added to 0.4 g of sample in a 10 mm NMR tube, approximately 3 mL of a 50/50 mixture of 0.025 M tetrachloroethane-d2 / orthodichlorobenzene (relaxation agent) in chromium acetylacetonate. Prepare by. The head space of the tube is purged of oxygen by replacing with pure nitrogen. Dissolve and homogenize the sample by heating the tube and its contents to 150 ° C. with periodic reflux initiated by a heat gun.

  After data collection, the chemical shift is internally referenced to 21.90 ppm mmmm pentad.

For metallocene propylene / ethylene copolymers, the integration procedure assigned in Journal of Macromolecular Chemistry and Physics, “Reviews in Macromolecular Chemistry and Physics”, C29 (2 & 3), 201-3 17, (1989) is used using the following procedure: Used to calculate the percent ethylene in the polymer.

  As indicated above, embodiments of the present invention provide a new class of propylene and α-olefin block interpolymers. These block interpolymers are characterized by an average block index of greater than 0, preferably greater than 0.2. Because of these block structures, these block interpolymers have a unique combination of properties or characteristics not found in other propylene / α-olefin copolymers. In addition, these block interpolymers contain various fractions with different block indices. Such a distribution of block indices impacts the overall physical properties of the block interpolymer. By adjusting the polymerization conditions, the distribution of the block index can be changed, thereby providing the ability to tailor the desired polymer. Such block interpolymers have many end uses. For example, these block interpolymers can be used in the production of polymer blends, fibers, films, molded articles, lubricants, base oils, and the like. Other advantages and features will be apparent to those skilled in the art.

  Although the present invention has been described with respect to a limited number of embodiments, the specific features of one embodiment should not be considered as belonging to other embodiments of the present invention. There is no single embodiment that represents all aspects of the invention. In some embodiments, a composition or method may include a number of compounds or steps not mentioned herein. In other embodiments, the composition or method is free or substantially free of any compounds or steps not listed herein. There are variations and modifications of the described embodiments. The method for producing the resin is described as including several actions or steps. These steps or actions can be performed in any order or sequence unless otherwise indicated. Finally, any number disclosed herein should be construed as meaning approximately, regardless of whether the word “about” or “approximately” is used in the description of the number. The appended claims are intended to cover all modifications and variations that fall within the scope of the invention.

Claims (36)

A propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, characterized by an average block index greater than zero to about 1.0 and a molecular weight distribution M _w / M _n greater than about 1.3 A propylene / α-olefin interpolymer. A propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, wherein the average block index is greater than 0 but less than about 0.4, and the molecular weight distribution M _w / M _n is about 1.3. A propylene / α-olefin interpolymer.   The propylene / α-olefin interpolymer according to claim 1 or 2, wherein the average block index is in the range of about 0.1 to about 0.3.   The propylene / α-olefin interpolymer of claim 1, wherein the average block index is in the range of about 0.4 to about 1.0.   The propylene / α-olefin interpolymer of claim 1, wherein the average block index is in the range of about 0.3 to about 0.7.   The propylene / α-olefin interpolymer of claim 1, wherein the average block index is in the range of about 0.6 to about 0.9.   The propylene / α-olefin interpolymer of claim 1, wherein the average block index is in the range of about 0.5 to about 0.7.   3. The propylene / [alpha] -olefin interpolymer of claim 1 or 2 having a density less than about 0.89 g / cc.   The propylene / α-olefin interpolymer of claim 1 or 2, having a density in the range of about 0.85 g / cc to about 0.905 g / cc.   The α-olefin is styrene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene or a combination thereof. 2. The propylene / α-olefin interpolymer according to 2.   The propylene / α-olefin interpolymer according to claim 1 or 2, wherein the α-olefin is 1-butene.   The propylene / α-olefin interpolymer according to claim 1 or 2, wherein the α-olefin is 1-octene. The propylene / α-olefin interpolymer according to claim 1 or 2, wherein M _w / M _n is greater than about 1.5. 3. The propylene / [alpha] -olefin interpolymer of claim 1 or 2, wherein _Mw / _Mn is greater than about 2.0. The propylene / α-olefin interpolymer according to claim 1 or 2, wherein M _w / M _n is from about 2.0 to about 8. The propylene / α-olefin interpolymer according to claim 1 or 2, wherein M _w / M _n is from about 1.7 to about 3.5. 3. The propylene / propylene according to claim 1 or 2, characterized by at least one melting point Tm expressed in degrees Celsius and a comonomer content expressed in weight%, wherein the numerical values of Tm and α-olefin correspond to the following relationship: α-olefin interpolymer:
_Tm > -2.909 (wt% α-olefin) +141.57. Characterized by an elastic recovery rate Re, expressed in percent measured in one cycle and 300 percent strain in a compression molded film of the propylene / α-olefin interpolymer, and a density d expressed in grams / cubic centimeter, Re and The propylene / α-olefin interpolymer according to claim 1 or 2, wherein the numerical value of d satisfies the following relationship when the propylene / α-olefin interpolymer is substantially free of a crosslinked phase:
Re> 1481-1629 (d). A propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, characterized in that it has at least one fraction obtained by a temperature rising elution fractionation method (“TREF”), A propylene / α-olefin interpolymer having a block index greater than about 0.3 and up to about 1.0 and having a molecular weight distribution M _w / M _n greater than about 1.3. A propylene / α-olefin interpolymer comprising polymerized units of propylene and α-olefin, characterized in that it has at least one fraction obtained by TREF, said fraction being greater than about 0 and about 0.4 A propylene / α-olefin interpolymer having a block index up to and having a molecular weight distribution M _w / M _n of greater than about 1.3.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.4.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.5.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.6.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.7.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.8.   21. The propylene / [alpha] -olefin interpolymer of claim 19 or 20, wherein the block index of the fraction is greater than about 0.9.   21. Propylene / [alpha] -olefin interpolymer according to claim 1, 2, 19 or 20, wherein the propylene content is greater than 50 mole percent.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, comprising one or more hard segments and one or more soft segments.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, wherein the hard segment is present in an amount from about 5% to about 85% of the interpolymer.   21. A propylene / [alpha] -olefin interpolymer according to claim 1, 2, 19 or 20, wherein the hard segment comprises at least 98% propylene by weight.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, wherein the soft segment comprises less than 95% propylene by weight.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, wherein the soft segment comprises less than 75% propylene by weight.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, comprising at least 10 hard and soft segments connected in a linear fashion to form a straight chain.   34. The propylene / [alpha] -olefin interpolymer of claim 33, wherein the hard and soft segments are randomly distributed along the chain.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, wherein the soft segment does not include a chip segment.   21. The propylene / [alpha] -olefin interpolymer of claim 1, 2, 19 or 20, wherein the hard segment does not include a chip segment.