JP6820957B2 - Polymer blend - Google Patents

Description

Various embodiments of the present invention are buffer tubes, core tubes, or slotted core fiber optic cables made from an extrudable blend of crystalline polypropylene modified with one or more crosslinked or crosslinkable impact modified polymers. Regarding components.

Optical fibers transmit information efficiently over long distances at high speeds. These fibers are delicate and must be protected. In practical applications, fiber optic cables protect the fibers from harmful environmental conditions such as mechanical damage and / or exposure to moisture. For example, specific protective components include extruded buffer tubes, core tubes, and slotted core members.

A buffer tube, also known as a loose buffer tube, is a protective component used to house and protect an optical fiber in a cable or the like. Typically, these loose buffer tubes are filled with hydrocarbon gels or greases to suspend the fibers and protect them from moisture, with high breakdown resistance, microbend resistance, low embrittlement temperature, good. Has stringent requirements for good grease compatibility, impact resistance, and low post-extrusion shrinkage. Materials used in the manufacture of buffer tubes include polybutylene terephthalate (“PBT”), high crystallinity polypropylene, and, to a lower degree, high density polyethylene. Since PBT is a costly material, a cost effective alternative is desired.

One embodiment is an extruded optical cable protection component.
(A) Crystalline polypropylene with a crystallinity of at least 55 percent,
(B) Containing extruded polymer blends, including crosslinked impact modified polymers.
The crosslinked impact modified polymer is an extruded optical cable protection component, which is an elastomer selected from the group consisting of crosslinked silane functionalized elastomers, crosslinked myrene anhydride functionalized elastomers, or combinations thereof.

Another embodiment is a polymer blend,
(A) Crystalline polypropylene with a crystallinity of at least about 55 percent,
(B) Impact-modified polymers selected from the group consisting of silane-grafted polyolefin elastomers, silane-grafted olefin multi-block interpolymers, silane-grafted olefin block composites, and combinations of two or more of them.
A polymer blend comprising (c) a non-silane grafted elastomer selected from the group consisting of olefin multiblock interpolymers, olefin block composites, and combinations thereof, and (d) a condensation catalyst.

Please refer to the attached drawing.

A cross-sectional view of a loose buffer tube optical fiber cable is shown. A partial cut-out view of the core tube optical fiber cable is shown. A cross-sectional view of a core optical fiber cable with a slot is shown.

Various embodiments of the present invention relate to polymer blends comprising crystalline polypropylene and crosslinked impact modified polymers. The polymer blend can optionally further include a non-crosslinking compatibilizer. The polymer blend may also contain one or more additives. Such polymer blends can be extruded to form fiber optic cable protection components.

Crystalline Polypropylene The crystalline polypropylene suitable for use in various embodiments may be homopolymeric polypropylene, either isotactic or syndiotactic. In one or more embodiments, the crystalline polypropylene may be isotactic homopolymer polypropylene in order to maximize the crystallinity of the polymer. A "polymer" is a macromolecular compound prepared by reacting (ie, polymerizing) the same or different types of monomers. "Polymer" includes homopolymers and interpolymers. As used herein, "homomopolymer" means a polymer containing repeating units derived from a single monomer species, but in addition to the residual amounts used in the preparation of homopolymers such as chain transfer agents. Does not exclude the compounds of.

The polypropylene used in the present invention is well known in the literature and can be prepared by known techniques. In general, polypropylene can be made using a Ziegler-Natta catalyst or a metallocene catalyst. "Kirk-Othmer Encyclopedia of Chemical Technology" (2001) describes these catalysts and their corresponding reactor processes for making crystalline polypropylene.

The crystallinity of polypropylene is measured by differential scanning calorimetry (“DSC”). In this measurement, a small amount of propylene polymer sample is encapsulated in an aluminum DSC pan. The sample is placed in a nitrogen-purged DSC cell at 25 cm / min and cooled to about -100 ° C. Heating to 225 ° C. at 10 ° C./min establishes a standard thermal history of the sample. The sample is then recooled to about −100 ° C. and reheated to 225 ° C. at 10 ° C./min. The heat of fusion (ΔH _observed ) observed in the second scan is recorded. The heat of fusion observed is related to the degree of crystallinity in weight percent based on the weight of the polypropylene sample by the following equation:
Crystallinity percent = (ΔH _observed ) / (ΔH _{isotactic pp} ) X100
In the formula, the heat of fusion (ΔH _{isotactic pp} ) of isotactic polypropylene is 165 joules per gram of polymer (J) in B. Wunderlich, Macromolecular Physics, Volume 3, Crystal Melting, Academic Press, New York, 1960, p48. / G) is reported. In various embodiments, the crystalline polypropylene can have a crystallinity of at least 55 weight percent, at least 65 weight percent, at least 70 weight percent, or at least 73 weight percent. U.S. Pat. No. 7,087,680, filed October 7, 2003, discloses examples of highly crystalline polypropylene useful in various embodiments of the present invention.

In one or more embodiments, crystalline polypropylene is 1 to 20 grams / 10 minutes (“g / 10 minutes”), 1 to 12 g / 10 minutes, 2 g to 9 g / 10 minutes, 2 to 8 g / 10 minutes, Alternatively, it can have a melt index (I ₂ ) in the range of 3-6 g / 10 min. The melt index provided herein is determined according to ASTM method D1238. Unless otherwise stated, the melt index (ie, I ₂ ) is determined at 190 ° C. and 2.16 kg.

In various embodiments, crystalline polypropylene is 45-95% by weight (“% by weight”), 55-90% by weight, 60-90% by weight, or 70-90% by weight based on the total weight of the polymer blend. It may be present in the polymer blend in a range of amounts.

In various embodiments, the nucleating agent may be used with crystalline polypropylene. Examples of suitable nucleating agents include ADK NA-11 and ADK NA-21, which are commercially available from Asahi Denim Kokai. Other examples include the nucleating agents described in US Pat. Nos. 3,367,926 and 5,574,816. Those skilled in the art can easily identify other useful nucleating agents. The nucleating agent is typically incorporated into crystalline polypropylene at a level of at least 500 ppm, at least 650 ppm, or at least 750 ppm.

Crosslink Impact Modified Polymers As mentioned above, polymer blends include crosslinked impact modified polymers. As used herein, a "shock-modifying polymer" is a polymer that modifies various properties of the crystalline polypropylene described above. For example, impact-modified polymers can absorb mechanical energy without crushing, thereby modifying crystalline polypropylene so as to impart sufficient impact toughness to the fiber optic cable.

In one or more embodiments, the crosslinked impact modified polymer is an elastomer. Crosslinked elastomers can be prepared from any known or upcoming elastomers such as olefin elastomers, olefin multiblock interpolymers, olefin block composites, or combinations of two or more of these. Such elastomeric components may be crosslinked using known cross-linking techniques such as silane cross-linking and maleic anhydride / amination cross-linking. In various embodiments, the crosslinked impact-modified polymer (ie, "crosslinkable" impact-modified polymer) can first be polymer blended with the crystalline polypropylene described above and any other desired component. The impact modified polymer can then be crosslinked in situ in the polymer blend. Therefore, the preferred cross-linking method selectively cross-links the impact modified polymer while not cross-linking other components of the polymer blend, such as crystalline polypropylene or other optional polymer components, or otherwise it. It does not have an adverse effect. In various embodiments, the cross-linking method used does not include peroxide-induced cross-linking.

As mentioned above, the impact-modified polymer to be crosslinked may be an olefin elastomer. Olefin elastomers include both polyolefin homopolymers and interpolymers. These olefin elastomers exclude the olefin multiblock interpolymer elastomers described below and the olefin block composite elastomers. Examples of polyolefin homopolymers are ethylene and propylene homopolymers. Examples of polyolefin interpolymers are ethylene / α-olefin interpolymers and propylene / α-olefin interpolymers. In such embodiments, the α-olefin may be a C _3-20 linear, branched, or cyclic α-olefin (in the case of a propylene / α-olefin interpolymer, the ethylene is an α-olefin. To be considered). Examples of C _3-20 α-olefins are propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene can be mentioned. The α-olefin may also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. Although not an α-olefin in the conventional sense of this term, for the purposes of the present invention, certain cyclic olefins such as norbornene and related olefins are α-olefins and some of the aforementioned α-olefins. Alternatively, it may be used instead of all. Similarly, styrene and related olefins (eg, α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Exemplary polyolefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene and the like. Exemplary terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene, and ethylene / butene / styrene. The copolymers may be random or blocky, but they are not olefin multiblock copolymers or olefin block composites, as described above.

Olefin elastomers can also contain one or more functional groups such as unsaturated esters or acids or silanes, these elastomers (polyolefins) are well known and can be prepared by conventional high pressure techniques. The unsaturated ester may be an alkyl acrylate, an alkyl methacrylate, or a vinyl carboxylate. The alkyl group can have 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. The carboxylate group can have 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. The portion of the copolymer due to the ester comonomer may range from 1 percent up to 50 weight percent based on the weight of the copolymer. Examples of acrylates and methacrylates are ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate. Examples of vinyl carboxylates are vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of unsaturated acids include acrylic acid or maleic acid. An example of an unsaturated silane is vinyl trialkoxysilane.

Functional groups may also be included in the olefin elastomer by grafting that can be achieved as is generally known in the art. In one embodiment, grafting is typically performed by free radical functionalization, which comprises melt blending a compound containing an olefin polymer, a free radical initiator (peroxide, etc.), and a functional group. You may. During the melt blend, the free radical initiator reacts with the olefin polymer (reactive melt blend) to form polymer radicals. The functional group-containing compound binds to the main chain of polymer radicals to form a functionalized polymer. Exemplary compounds containing functional groups include, but are limited to, alkoxysilanes (eg, vinyltrimethoxysilane, vinyltriethoxysilane), and vinylcarboxylates, and anhydrides (eg, maleic anhydride). Not done.

As a more specific example of an optional olefin elastomer useful in the present invention, an ultra-low density polyethylene (“VLDPE”) (eg, FLEXOMER ™ ethylene / 1-hexene polyethylene made by The Dow Chemical Company). ), Uniformly branched, linear ethylene / α-olefin copolymers (eg, TAFMER ™ by Mitsui Polyethylene Company Limited and EXACT ™ by EXxon Chemical Company), and uniformly branched, substantially linear. Ethylene / α-olefin polymers such as AFFINITY ™ and ENGAGE ™ polyethylene available from The Dow Chemical Company.

Olefin elastomers can also include ethylene-propylene-diene monomer (“EPDM”) elastomers and chlorinated polyethylene (“CPE”). Examples of suitable EPDMs on the market include NORDEL ™ EPDM available from The Dow Chemical Company. Examples of suitable CPEs on the market include TYRIN ™ CPE available from The Dow Chemical Company.

The olefin elastomers useful herein are also propylene, butene, and other alkene-based copolymers, such as the majority of units derived from propylene and a few units derived from another α-olefin (including ethylene). Also includes copolymers containing and. Illustrative propylene-based polymers useful herein include VERSIFY ™ polymers available from The Dow Chemical Company and VISTAMAXX ™ polymers available from ExxonMobil Chemical Company.

Olefin elastomers, in particular ethylene elastomers, before grafting, may have a density of less than 0.91 g / cm ³ or less than 0.90 g / cm ^3. Olefin elastomers suitable for use herein, especially ethylene copolymers, can have densities greater than 0.85 g / cm ³ or greater than 0.86 g / cm ³ .

Olefin elastomers, especially ethylene elastomers, can have a melt index (I ₂ ) greater than 0.10 g / 10 min or greater than 1 g / 10 min prior to grafting. Olefin elastomers, especially ethylene elastomers, can have a melt index of less than 500 g / 10 min or less than 100 g / 10 min.

As mentioned above, the impact modified polymer to be crosslinked may be an olefin multiblock interpolymer. An "olefin multiblock interpolymer" is preferably a polymer containing two or more chemically distinct regions or segments (referred to as "blocks") that are linearly bonded, ie in a suspended or grafted mode. Instead, it is a polymer containing a polymerized olefin functional group, preferably a chemically distinguishable unit attached end-to-end to an ethylene functional group. In various embodiments, the block comprises the amount or type of comonomer incorporated, the density, the amount of crystallinity, the size of microcrystals due to the polymer of such composition, the type or degree of stereoregularity (isotactic). Or syndiotactic), regio-regularity or regio-irregularity, amount of branching (including long-chain or super-branching), uniformity, or any other chemical or physical property. Compared to prior art block interpolymers, including interpolymers produced by sequential monomer addition, flow catalysts, or anionic polymerization techniques, the multiblock interpolymers used in the practice of the present invention are, in preferred embodiments, them. Unique distribution, block of polydispersity (PDI or M _w / M _n or MWD) of both polymers due to the effect of the shuttling agent (s) combined with multiple catalysts used in the preparation of It features a long distribution and / or a block number distribution. More specifically, when produced in a continuous process, the polymer can be 1.4-3.5, 1.5-2.5, 1.6-2.5, or 1.6-2.1. You can have a PDI. When produced in a batch or semi-batch process, the polymer has a PDI of 1.4-2.9, 1.4-2.5, 1.4-2.0, or 1.4-1.8. be able to.

In various embodiments, the olefin multiblock interpolymer may be an ethylene multiblock interpolymer. The term "ethylene multi-block interpolymer" means a multi-block interpolymer containing ethylene and one or more copolymerizable comonomer, where ethylene is a plurality of polymers of at least one block or segment in the polymer. It can constitute a monomer unit and make up at least 90, at least 95, or at least 98 mol% (“mol%”) of the block. Based on the total weight of the polymer, the ethylene multiblock interpolymers used herein can have an ethylene content of 25-97 mol%, 40-96 mol%, 55-95 mol%, or 65-85 mol%. it can. The comonomer (s) or comonomer (s) can constitute the rest of the interpolymer. In one or more embodiments, the olefin multiblock interpolymer may be an olefin multiblock copolymer.

In some embodiments, the ethylene multiblock interpolymer can be represented by the following formula:
(AB) _n
In the formula, n is at least 1, preferably 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more. It is a larger integer, where "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, A and B are connected in a linear fashion rather than in a branched or star style. A "hard" segment refers to a block of polymerized units in which ethylene is present in an amount of more than 95 weight percent, preferably more 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, the hard segment comprises all or substantially all ethylene. On the other hand, the "soft" segment is a block of polymerized units of ethylene and α-olefin comonomer with a comonomer content of greater than 5% by weight, greater than 8% by weight, greater than 10% by weight, or greater than 15% by weight. Point to. In some embodiments, the comonomer content in the soft segment is greater than 20% by weight, greater than 25% by weight, greater than 30% by weight, greater than 35% by weight, greater than 40% by weight, greater than 45% by weight, 50% by weight, Alternatively, it may be more than 60% by weight.

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

In other embodiments, block interpolymers usually do not have a third type of block. In yet another embodiment, each of block A and block B has a monomer or comonomer randomly distributed within the block. In other words, neither block A nor block B contains two or more segments (or subblocks) of different compositions, such as tip segments that have a different composition than the rest of the block.

Since each identifiable segment or block formed from two or more monomers is attached to a single polymer chain, it is not possible to completely separate the polymer using standard selective extraction techniques. Can not. For example, polymers containing relatively crystalline regions (high density segments) and relatively amorphous regions (low density segments) can be selectively extracted or fractionated using different solvents. Can not. In various embodiments, the amount of polymer that can be extracted using either the dialkyl ether or the alkane solvent is less than 10 percent, less than 7 percent, less than 5 percent, or less than 2 percent of the total weight of the polymer.

In some embodiments, the multiblock interpolymer has a PDI that fits the Schultz-Flory distribution rather than the Poisson distribution. The interpolymer is further characterized by having both a polydisperse block distribution and a block size polydisperse distribution, and having the most probable distribution of block lengths. Preferred multi-block interpolymers are those containing four or more blocks or segments, including terminal blocks. More preferably, the interpolymer comprises at least 5, 10, or 20 blocks or segments, including terminal blocks.

In a further embodiment, the olefin multiblock interpolymers of the invention, especially those made in a continuous solution polymerization reactor, have the most probable distribution of block lengths. In one embodiment of the invention, the olefin multiblock interpolymer has M _w / M _n of about 1.7 to about 3.5, as well as
(A) Defined to have at least one melting point T _m (temperature in degrees Celsius) and density d (grams / cubic centimeter), in which case the values of T _m and d correspond to the following relationships?
T _m > -6553.3 + 13735 (d) -7051.7 (d) ² , or (B) heat of fusion ΔH (J / g), and maximum differential scanning calorimetry (“DSC”) peak and maximum crystallization analysis It features a delta amount of ΔT (temperature in degrees Celsius) defined as the temperature difference from the picture (“CRYSTAF”) peak, in which case the values of ΔT and ΔH have the following relationship:
For ΔH greater than zero and up to 130 J / g, ΔT> -0.1299 (ΔH) +62.81
For ΔH greater than 130 J / g, ΔT> 48 ° C.
In this case, the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (ie, the peak must mean at least 5 percent of the cumulative polymer) and less than 5 percent of the polymer can be identified as a CRYSTAF peak. If so, the CRYSTAF temperature is 30 ° C., or (C) 300 percent strain and elastic recovery Re (percent) in one cycle, measured using compression molded films of olefin multiblock interpolymers, and density d. If the olefin multiblock interpolymer has (grams / cubic centimeter) and in this case the olefin multiblock interpolymer contains substantially no crosslinked phase, the values of Re and d satisfy the following relationship or
The Morcomonomer content of the Re> 1481-1629 (d), or (D) fraction is at least 5% higher or at least 10% higher than that of the comparable random ethylene interpolymer fraction that elutes at the same temperature. Has a molecular weight fraction that elutes at 40 ° C. to 130 ° C. when fractionated using a heated elution fraction (“TREF”), characterized by having a comparable random ethylene monomer. The polymer has the same comonomer (s) and has a melt index, density, and molcomonomer content (based on the entire polymer) of less than 10% of that of the olefin multiblock interpolymer, or (E). It has a storage elasticity G'(25 ° C) at 25 ° C and a storage elasticity G'(100 ° C) at 100 ° C, in which case the ratio of G'(25 ° C) to G'(100 ° C). Is characterized by an average block index in the range of about 1: 1 to about 9: 1 or (F) greater than zero and up to about 1.
The olefin multiblock interpolymer may have one, some, all, or any combination of the properties (A)-(F).

Suitable monomers for use in the preparation of olefin multiblock interpolymers used in the practice of the present invention include ethylene and one or more additional polymerizable monomers other than ethylene. Examples of suitable comonomers are linear or branched α-olefins of 3 to 30, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-Hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eikosen, Cycloolefins with 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4. 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, diolefins and polyolefins such as butadiene, isopene, 4-methyl-1,3-pentadiene, 1,3 -Pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4 octadiene, 1,5-octadien, 1,6-octadien, 1,7-octadene, etilidennorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, and 5,9-dimethyl-1,4 , 8-Decatrene, and 3-phenylpropene, 4-phenylpropene, 1,2-difluoroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1-propene.

Olefin multiblock interpolymers may be modified by, for example, grafting, hydrogenation, nitrene insertion reactions, or other functionalization reactions such as those known to those of skill in the art. A preferred functionalization is a grafting reaction using a free radical mechanism. Species that can be grafted by various radicals may adhere to the polymer individually or as relatively short grafts. These species contain unsaturated molecules, each containing at least one heteroatom. These species include maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalanhydride, bromomaleic anhydride, chloromaleic acid. Anhydrides, nadonic anhydrides, methylnadonic anhydrides, alkenylsuccinic anhydrides, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, and their respective esters, imides, salts, and Includes, but is not limited to, the deal alder adduct of the compound. These species also include silane compounds.

The olefin multi-block interpolymer, less than 0.90 g / cm ^3, less than 0.89 g / cm ^3, less than 0.885 g / cm ^3, less than 0.88 g / cm ^3, or a density less than 0.875 g / cm ³ Can have. Olefin multi-block interpolymer is at least 0.85 g / cm ^3, it may have a density of at least 0.86 g / cm ^3, or at least 0.865 g / cm ^3,. Density is measured by the procedure of ASTM D792.

The olefin multiblock interpolymer can have a melt index of at least 0.1 g / 10 min, at least 0.2 g / 10 min, or at least 0.3 g / 10 min. In various embodiments, the olefin multiblock interpolymer can have a melt index of less than 20 g / 10 minutes, less than 10 g / 10 minutes, less than 7 g / 10 minutes, or less than 1 g / 10 minutes. In one or more embodiments, the olefin multiblock interpolymer can have a melt index in the range of 0.38 to 0.62 g / 10 min.

The olefin multiblock interpolymers useful herein can have a 2% secant coefficient of less than 150 MPa, less than 100 MPa, less than 50 MPa, or less than 10 MPa as measured according to ASTM D790. Olefin multiblock interpolymers can have a 2% secant coefficient greater than zero.

Olefin multiblock interpolymers useful herein are below 125 ° C, but may have melting points above 60 ° C, above 70 ° C, above 80 ° C, above 90 ° C, above 100 ° C, or above 110 ° C. it can. The melting point is measured by the differential scanning calorimetry (“DSC”) method described in WO 2005/090427 (US Patent Application Publication No. 2006/0199930).

The olefin multiblock interpolymer is 1,000 to 5,000,000 g / mol, 1,000 to 1,000,000 g / mol, 10,000 to 500,000 g / mol, or 10,000 to 300,000 g / mol. It can have a weight average molecular weight of mol (“M _w ”).

In one or more embodiments, the olefin multiblock interpolymer contains 10-40% by weight, 15-25% by weight, or 15-17% by weight of hard segments. The hard segment does not contain units derived from comonomer or contains 0.5 mol%. The olefin multiblock interpolymer also contains 60-90% by weight, or 75-85% by weight, or 83% -85% by weight of soft segments. The content of the α-olefin in the soft block may be in the range of 20 to 40 mol%, 25 to 35 mol%, or 23 to 30 mol%. In various embodiments, the monomer may be ethylene and the comonomer may be butene or octene. In some embodiments, the comonomer is octene. The comonomer content is measured by nuclear magnetic resonance (“NMR”) spectroscopy.

In various embodiments, the olefin multiblock interpolymer may be mesophase separated. As used herein, "intermediate phase separation" means the process by which polymer blocks separate locally to form regular domains. Crystallization of ethylene segments in these systems is primarily limited to the resulting intermediate phase, and such systems may be referred to as "intermediate phase separated". These intermediate phases can take other known forms for spheres, cylinders, lamellae, or block interpolymers. For example, the narrowest dimension of the domain in the direction perpendicular to the plane of the lamella is generally greater than about 40 nm in the mesophase separated olefin multiblock interpolymer of the present invention.

The size of the domain may be in the range of 40-300 nm, 50-250 nm, or 60-200 nm as measured in the direction perpendicular to the plane of the lamella, or by a minimum dimension such as the diameter of a sphere or cylinder. In addition, it may have minimum dimensions greater than 60 nm, greater than 100 nm, and greater than 150 nm. Domains may be characterized as other known forms for cylinders, spheres, lamellae, or block interpolymers.

The mesophase separated polymer contains an olefin multi-block interpolymer, and the amount of comonomer in the soft segment when compared to the amount of comonomer in the hard segment causes the block interpolymer to experience mesophase separation in the melt. Is such an amount. The amount of comonomer required may be measured in mole percent and will vary from comonomer to comonomer. Calculations can be made for any desired comonomer to determine the amount required to achieve mesophase separation. The lowest level of incompatibility to achieve mesophase separation in these polydisperse block interpolymers is expressed as χN and is predicted to be χN = 2.0 (I.I. Potemkin, S.V. Panyukov, Phys. Rev. E. 57, 6902 (1998)). Recognizing that fluctuations usually push the order-disorder transition of commercially available block copolymers to slightly higher χN, the value χN = 2.34 is used as the minimum value in the following calculations. D. J. Lohse, W. et al. W. Graysley, Polymer Blends Volume 1: Formulation, ed. D. R. Paul, C.I. B. Converting χN to the product of χ / v and M / ρ (in the equation, v is the reference volume, M is the number average block molecular weight, and ρ is the melt density) according to the Bucknall, 2000 approach. Can be done. The melt density is considered to be 0.78 g / cm ³ , and a typical block molecular weight value is about 25,000 g / mol based on the diblock with a total molecular weight of 51,000 g / mol. Χ / v when the comonomer is butene or propylene is obtained by using 130 ° C. as the temperature and then interpolating or extrapolating the data provided in Table 8.1 in the references by Lohse and Graysley. It is determined. For each comonomer type, a linear regression was performed on the mole percent of comonomer. If the octene is a comonomer, Reichart, G. et al. C. The same procedure was performed using data from et al, Macromolecules (1998), 31,7886. The entangled molecular weight (kg / mol) at 413K (about 140 ° C.) is considered to be 1.1. Using these parameters, if the comonomer is octene, butene, or propylene, the minimum difference in comonomer content is determined to be 20.0, 30.8, or 40.7 mol percent, respectively. .. When the comonomer is 1-octene, the difference in octene mol% (delta octene) between the hard and soft segments is at least 20.0 mol%, at least 22 mol%, at least 23 mol%, at least 24 mol%, at least 25 mol. %, Or at least 26 mol%. Further, the Δoctene value may be in the range of 20.0 to 60 mol% or 22 to 45 mol%. When the comonomer is 1-butene, the difference in mol% of butene (Δ-butene) between the hard and soft segments is at least 30.8 mol%, at least 33.9 mol%, at least 35.4 mol%, at least 36. It can be 9.9 mol%, at least 38.5 mol%, or at least 40.0 mol%. Further, the Δ butene value may be in the range of 30.8 to 80 mol%, 33.9 to 60 mol%, 36 to 50 mol%, or 37 to 40 mol%. When the comonomer is propylene, the difference in mol% of propylene (Δpropylene) between the hard and soft segments is at least 40.7 mol%, at least 44.7 mol%, at least 46.8 mol%, at least 48.8 mol. %, At least 50.9 mol%, or at least 52.9 mol%. Further, the Δpropylene value may be in the range of 40.7 to 95 mol%, 44.7 to 65 mol%, or 48.8 to 60 mol%.

In some embodiments, the olefin multiblock interpolymer can have an average block index (“ABI”) greater than zero but less than 0.4 or 0.1 to 0.3. In other embodiments, the ABI may be greater than 0.4 and up to 1.0. In some embodiments, the ABI may range from 0.4 to 0.7, 0.5 to 0.7, or 0.6 to 0.9. In yet other embodiments, the ABI is 0.3-0.9, 0.3-0.8, or 0.3-0.7, 0.3-0.6, 0.3-0.5. , Or may be in the range of 0.3 to 0.4. In still other embodiments, the ABIs are 0.4-1.0, 0.5-1.0, 0.6-1.0, 0.7-1.0, 0.8-1.0, Alternatively, it may be in the range of 0.9 to 1.0.

The olefin multiblock interpolymers used in the practice of the present invention, their preparation and use, and methods for calculating specific properties (ABI, etc.) are described in US Pat. No. 7,947,793 and US Patent Application Publication. It is fully described in No. 2010/0113698A1.

Commercially available olefin multiblock interpolymers suitable for use herein include, but are not limited to, INFUSE ™ 9077 available from The Dow Chemical Company, Midland, Michigan, USA.

As mentioned above, the impact modified polymer to be crosslinked may be an olefin block composite. The term "block composite" refers to a polymer composition comprising three components: (1) a soft copolymer, (2) a hard polymer, and (3) a block copolymer having soft and hard segments. The hard segments of the block copolymer are the same composition as the hard polymer in the block copolymer, and the soft segments in the block copolymer are the same composition as the soft copolymer of the block composite.

The block copolymer present in the olefin block complex may be linear or branched. More specifically, when produced in a continuous process, the block complex can be 1.7-15, 1.8-3.5, 1.8-2.2, or 1.8-2.1. You can have a PDI. When produced in a batch or semi-batch process, the block complex has a PDI of 1.0-2.9, 1.3-2.5, 1.4-2.0, or 1.4-1.8. Can have. The term "olefin block complex" refers to a block complex prepared alone or substantially alone from two or more α-olefin monomers. In various embodiments, the olefin block complex may consist of only two α-olefin monomer units. Examples of olefin block complexes include hard segments and hard polymers containing only or substantially only propylene monomer residues, and soft segments and soft polymers containing only or substantially only comonomer residues of ethylene and propylene. Can be mentioned.

In describing the olefin block complex, the "hard" segment refers to a highly crystalline block of polymerized units in which a single monomer is present in an amount greater than 95 mol% or greater than 98 mol%. In other words, the comonomer content in the hard segment is less than 5 mol% or less than 2 mol%. In some embodiments, the hard segment comprises all or substantially all propylene units. On the other hand, the "soft" segment refers to a block of amorphous, substantially amorphous, or elastomeric of polymerized units with a comonomer content greater than 10 mol%. In some embodiments, the soft segment comprises an ethylene / propylene interpolymer.

When referring to block complexes, the term "polyethylene" includes homopolymers of ethylene and copolymers of ethylene with at least 50 mol% ethylene and one or more C _3-8 α-olefins. The term "propylene copolymer" or "propylene interpolymer" means a copolymer containing propylene and one or more copolymerizable comonomer, which is a plurality of at least one block or segment (crystalline block) in the polymer. The polymerized monomeric unit comprises propylene which can be present in an amount of at least 90 mol%, at least 95 mol%, or at least 98 mol%. Polymers made primarily from different α-olefins such as 4-methyl-1-pentene are also referred to similarly. The term "crystallinity", when used to describe an olefin block composite, refers to a primary transition or crystal melting point ("Tm") determined by differential scanning calorimetry ("DSC") or equivalent technique. Refers to a polymer or polymer block that has. The term "crystallinity" may be used synonymously with the term "semi-crystalline". The term "amorphous" refers to a polymer that does not have a crystalline melting point. “Isotactic” means a polymeric repeating unit having at least 70 percent isotactic pentad as determined by ¹³ C-nuclear magnetic resonance (“NMR”) analysis. By "highly isotactic" is meant a polymer having at least 90 percent isotactic pentad.

When referring to an olefin block composite, the term "block copolymer" or "segmented copolymer" includes two or more linearly bonded chemically distinct regions or segments (referred to as "blocks"). A polymer, i.e., a polymer that contains chemically distinct units attached end-to-end to a polymerized ethylene functional group rather than a suspended or grafted mode. In embodiments, the block is the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the size of microcrystals due to the polymer of such composition, the type or degree of stereoregularity (isotac). Tick or syndiotactic), regio-regularity or regio-irregularity, amount of branching, including long-chain or super-branching, homogeneity, or any other chemical or physical property. The olefin block complex used herein is, in a preferred embodiment, due to the effect of the shuttling agent (s) combined with the catalyst (s) used to prepare the block complex, the polymeric PDI. It is characterized by its unique distribution, block length distribution, and / or block number distribution.

The olefin block complex used herein is an addition-polymerizable monomer or a mixture of monomers that contains at least one addition polymerization catalyst, co-catalyst, and chain shuttling agent (“CSA”) under addition polymerization conditions. It can be prepared by a process involving contacting with a composition comprising, the process being in two or more reactors operating under steady-state polymerization conditions, or two of reactors operating under plug-flow polymerization conditions. It is characterized by the formation of at least some of the polymer chains that grow under different process conditions within one or more zones.

Suitable monomers for use in the preparation of the olefin block composites of the present invention include any addition-polymerizable monomers, such as any olefin or diolefin monomer containing any α-olefin. Examples of suitable monomers are linear or branched α-olefins of 2 to 30 or 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene. , 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Etc., and diolefins and polyolefins such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1 , 3-Hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, etilidennorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1 , 6-Octadiene, 4-ethylidene-8-methyl-1,7-nonadien, and 5,9-dimethyl-1,4,8-decatorien. In various embodiments, ethylene and at least one copolymerizable comonomer, propylene having 4 to 20 carbons and at least one copolymerizable comonomer, 1-butene having 2 or 5 to 20 carbons. And at least one copolymerizable comonomer, or 4-methyl-1-pentene having 4 to 20 carbons and at least one different copolymerizable comonomer may be used. In embodiments, the olefin block composite is prepared with propylene and ethylene monomers.

The comonomer content in the resulting block composite may be measured using any suitable technique such as NMR spectroscopy. Some or all polymer blocks are amorphous or relatively amorphous polymers such as propylene, 1-butene, or copolymers of 4-methyl-1-pentene and commonomer, especially propylene containing ethylene, 1 A random copolymer of −butene, or 4-methyl-1-pentene, if present, with any remaining polymer block (hard segment) in polymerized form, propylene, 1-butene or 4-methyl-1-pentene. It is highly desirable to mainly include. Preferably, such hard segments are highly crystalline or stereospecific polypropylene, polybutene or poly-4-methyl-1-pentene, especially isotactic homopolymers.

In addition, the block copolymer of the block composite comprises 10-90% by weight of hard segments and 90-10% by weight of soft segments.

Within the soft segment, the molar percentage of comonomer may be in the range of 5 to 90% by weight, or 10 to 60% by weight. If the comonomer is ethylene, it may be present in an amount of 10-75% by weight, or 30-70% by weight. In embodiments, propylene constitutes the rest of the soft segment.

In embodiments, the block copolymer of the olefin block composite comprises a hard segment of 80-100% by weight propylene. The hard segment may be greater than 90% by weight, greater than 95% by weight, or greater than 98% by weight of propylene.

The block complexes described herein may be distinguished from conventional random copolymers, physical blends of polymers, and block copolymers prepared by sequential monomer addition. The block composite was improved from the random copolymer by features such as higher melting temperature, block composite index, etc. than the same amount of comonomer, block composite index at lower temperature, better tensile strength, as described below. There is block polydispersity from physical blends due to features such as breaking strength, finer morphology, improved optical properties, and greater impact strength, by molecular weight distribution, rheology, shear fluidization, leology ratios, and block polydispersity. May be distinguished from block copolymers prepared by sequential monomer addition.

In some embodiments, the block complex has a block complex index (“BCI”) as defined below, i.e. greater than zero and less than 0.4, or 0.1 to 0.3. .. In other embodiments, the BCI is greater than 0.4 and up to 1.0. Further, the BCI may be in the range of 0.4 to 0.7, 0.5 to 0.7, or 0.6 to 0.9. In some embodiments, the BCI is 0.3-0.9, 0.3-0.8, 0.3-0.7, 0.3-0.6, 0.3-0.5, Alternatively, it may be in the range of 0.3 to 0.4. In other embodiments, the BCI is 0.4-1.0, 0.5-1.0, 0.6-1.0, 0.7-1.0, 0.8-1.0, or It may be in the range of 0.9 to 1.0. BCI is defined herein as equal to the weight percent (ie, weight fraction) of the diblock copolymer divided by 100%. The value of the block complex index may range from 0 to 1, where 1 is equal to 100% diblock and zero is the material, such as conventional blends or random copolymers. Methods for determining BCI can be found, for example, in paragraphs [0170]-[0189] of US Publication No. 2011/0282258.

The olefin block complex can have a Tm above 100 ° C, above 120 ° C, or above 125 ° C. The melt index of the block complex (“I ₂ ”) ranges from 0.1 to 1000 g / 10 min, 0.1 to 50 g / 10 min, 0.1 to 30 g / 10 min, or 1-10 g / 10 min. It may be. The block complex has a weight average molecular weight of 10,000 to 2,500,000, 35,000 to 1,000,000, 50,000 to 300,000, or 50,000 to 200,000 g / mol (“M”. _w ") can be possessed.

A process useful in producing an olefin block complex suitable for use in the present invention can be found, for example, in US Patent Application Publication No. 2008/0269412 published October 30, 2008. Suitable catalysts or catalyst precursors for use in the preparation of olefin block complexes are those disclosed in WO 2005/090426, specifically on page 20 from line 30 to page 53, line 20 and the like. Includes metal complexes of. Suitable catalysts are also published in US Patent Application Publication Nos. 2006/0199930, 2007/0167578, 2008/0311812, 2011/082258, US Pat. No. 7,355,089, and International Publication. It is also disclosed in No. 2009/012215. Suitable cocatalysts are those disclosed in WO 2005/090426, specifically those disclosed on page 54, line 1 to page 60, line 12. Suitable chain shuttling agents are those disclosed in WO 2005/090426, specifically those disclosed on page 19 from line 21 to page 20 on line 12. A particularly preferred chain shuttling agent is a diaquil zinc compound. The olefin block complex itself is fully described in US Pat. No. 8,476,366.

As mentioned above, the impact modified polymer can be crosslinked using a variety of methods. In embodiments, the aforementioned elastomers may include (i) silane grafting the elastomer, thereby forming a silanegrafted elastomer, and then cross-linking the silanegrafted elastomer in the presence of a water curing catalyst and water. Alternatively, it can be crosslinked by (ii) grafting the elastomer with maleic anhydride (“MAH”) and then cross-linking the MAH-grafted elastomer by amination cross-linking.

As just mentioned, one method of cross-linking a shock-modified polymer involves incorporating a silane functional group into the elastomer. Any silane that will effectively copolymerize with or graft to an elastomer selected from those described above can be used herein. In various embodiments, a silane comonomer having the following formula can be incorporated (ie, grafted or copolymerized) into the elastomer described above:

In the formula, R ¹ is a hydrogen atom or a methyl group, x is 0 or 1, provided that n is at least 1 when x is 1, and m and n are independent. It is an integer of 0 to 12 (including the boundary value), preferably 1 to 4, and each R ² is independently an alkoxy group having 1 to 12 carbon atoms (for example, methoxy, ethoxy, butoxy). , Aryloxy group (eg, phenoxy), Araloxy group (eg, benzyloxy), aliphatic acyloxy group with 1-12 carbon atoms (eg, formyloxy, acetyloxy, propanoyloxy), amino group or substituted It is a hydrolyzable organic group such as an amino group (for example, alkylamino, arylamino) or a lower alkyl group having 1 to 6 (including boundary values) carbon atoms, but of the three R groups. The condition is that one or less of the above is alkyl. Such silanes may be copolymerized in the reactor with the monomers forming the elastomeric compounds described above. Such silanes can also be grafted into suitable elastomers by the use of suitable amounts of organic peroxides. It also contains silanes that add unsaturatedity to the elastomer by a free radical process such as mercaptopropyltrialkoxysilane.

Suitable silanes include ethylenically unsaturated hydrocarbyl groups such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or γ- (meth) acrylicoxyallyl groups and, for example, hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino. Examples thereof include unsaturated silanes containing hydrolyzing groups such as groups. Examples of hydrolysis groups include methoxy group, ethoxy group, formyloxy group, acetoxy group, proprionyloxy group, and alkylamino group or arylamino group. Preferred silanes are unsaturated alkoxysilanes that can be grafted onto the polymer or copolymerized with other monomers (such as ethylene and acrylate) in the reactor. These silanes and their methods of preparation are more fully described in US Pat. No. 5,266,627 of Meverden et al. Vinyl trimethoxysilane (VTMS), vinyl triethoxysilane, vinyl triacetoxysilane, γ- (meth) acrylicoxypropyltrimethoxysilane, and mixtures thereof are preferred silane commonomers for use in the present invention.

The amount of silane comonomer used can vary widely depending on the nature of the polymer, the silane, the conditions of the treatment or reactor, the efficiency of grafting or copolymerization, the end application, and similar factors. However, typically at least 0.5, or at least 0.7% by weight, is used based on the total weight of the elastomer. Convenience and economic considerations are two of the major restrictions on the maximum amount of silane comonomer used, typically a maximum amount of silane comonomer of 5% or 3% by weight. Do not exceed.

The silane comonomer can be grafted onto the elastomer by any conventional or upcoming method, typically in the presence of a free radical initiator (eg, peroxide or azo compound), or by ionizing radiation. .. Examples of suitable free radical initiators include peroxide initiators such as dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl. Peroctate, methylethylketone peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauryl peroxide, and any one of tert-butylperacetate, etc. Examples include organic initiators. Suitable azo compounds are 2,2-azobisisobutyronitrile. The amount of initiator can vary, but is typically present in an amount of at least 0.04 parts / 100 parts of resin (“phr”), or at least 0.06 phr. Typically, the initiator does not exceed 0.15 phr, or 0.10 phr. The weight ratio of silane comonomer to initiator can also vary widely, but typically the weight ratio of comonomer: initiator is 10: 1 to 500: 1 or 18: 1 to 250: 1. When used in 100 parts / resin or ph, "resin" means the above-mentioned elastomer.

While conventional methods can be used to graft silanecomonomers onto elastomers, exemplary methods blend the two components with an initiator in the first stage of a reactor extruder such as a Buss kneader. Including doing. The grafting conditions may vary, but the melting temperature is typically 160-260 ° C, or 190-230 ° C, depending on the residence time and half-life of the initiator.

Copolymerization of the silane comonomer with the monomer used in the preparation of the above-mentioned elastomer may be carried out in the reactor (s) or the reactors (s) used for preparing the above-mentioned elastomer. Such copolymerization techniques are known to those of skill in the art.

Elastomers containing hydrolyzable silane functional groups can be crosslinked by the use of a condensation catalyst. The condensation catalyst may be any compound that catalyzes the water cross-linking reaction with the hydrolyzable silane group. Condensation catalysts can include carboxylates of metals such as tin, zinc, iron, lead, and cobalt, organic bases, inorganic acids, and organic acids. Examples of such catalysts are dibutyltin dilaurate (“DBTDL”), dibutyltin diacetate, dioctyltin dilaurate, tin acetate, tin caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethylamine, dibutylamine. , Inorganic acids such as hexylamine, pyridine, sulfuric acid and hydrochloric acid, and organic acids such as sulfonic acid (eg, toluenesulfonic acid), acetic acid, stearic acid, and maleic acid, but are not limited thereto. In various embodiments, the catalyst is selected from tin-based catalysts and sulfonic acids. In yet other embodiments, the catalyst may be tin carboxylate. Moreover, in certain embodiments, the catalyst is DBTDL. The catalyst may be used undiluted or as part of a masterbatch. Such a masterbatch may additionally contain, for example, a polyolefin carrier (eg, polyethylene), an antioxidant, and / or a metal inactivating agent. Examples of suitable commercially available catalyst-containing masterbatches include DFDA-5480NT ™ available from The Dow Chemical Company, Midland, Michigan, USA.

The minimum amount of condensation catalyst used is the amount of catalyst. Typically, this amount is at least 0.01% by weight, at least 0.02% by weight, or at least 0.03% by weight, based on the combined weight of the impact modified polymer and the condensation catalyst. The only limit to the maximum amount of cross-linking catalyst in a shock-modified polymer is imposed by economics and practicality (eg, diminishing yield), but typically the general maximum is Less than 5% by weight, less than 3% by weight, or less than 2% by weight, based on the combined weight of the impact modified polymer and the condensation catalyst. In various embodiments, the condensation catalyst may be present in the polymer blend in an amount in the range of 0.01-0.5% by weight, based on the total weight of the polymer blend.

As mentioned above, the alternative cross-linking method involves grafting or copolymerizing maleic anhydride with the elastomers described above in order to make a cross-linking impact-modified polymer. Grafting techniques are known in the art, and MAH comonomer can be grafted with the elastomers described above using any known method or methods found in the art. When MAH copolymers are used, high pressure reactor polymers containing ethylene, maleic anhydride, and optionally additional comonomer may be used. For example, ethylene / maleic anhydride / butyl acrylate terpolymer can be used as a MAH-containing copolymer. An example of such a terpolymer on the market is Rotadar AX 8840 by Arkema.

Whether copolymerized or grafted, MAH comonomer in impact-modified polymer is less than 0.25% by weight to more than 1.0% by weight, 0.25 based on the total weight of the elastomer. It can be present in an amount in the range of ~ 1.5% by weight, or 0.5 to 1.25% by weight.

The resulting MAH functionalized elastomer can be crosslinked by an amination process. In such a process, the MAH functionalized elastomer is combined with a diamine crosslinker, if in situ crosslinked (as described below), the crystalline polypropylene described above and any other desired component. Selective cross-linking of the MAH functionalized elastomer can then be achieved using either high temperature (eg, 180 ° C.) or an amine catalyst. In various embodiments, the MAH functionalized elastomer can be selectively crosslinked in situ by extrusion of the polymer blend at elevated temperatures.

Any known or upcoming diamine cross-linking agent may be used to selectively cross-link the MAH functionalized elastomer. Suitable examples include, but are not limited to, 1,12-diaminododecane, hexamethylenediamine, ethylenediamine, 2-methyl-1,5-pentanediamine, and 1,3-cyclohexanebis (methylamine). .. In various embodiments, the amount of diamine crosslinker used is 0.8-1.3, 0.9-1.2, or 1. per maleic anhydride functional group in the MAH functionalized elastomer. It may be in the range of 0 to 1.1 molar equivalents of amine groups. In one or more embodiments, the diamine crosslinker used may be present in the MAH functionalized elastomer in an amount of about 1.1 molar equivalents of amine groups per maleic anhydride functional group.

In one or more embodiments, the crosslinked impact modified polymer is 4-50% by weight, 4-30% by weight, 4-25% by weight, 4-20% by weight, or 4-20% by weight, based on the total weight of the polymer composition. It may be present in the polymer composition in an amount in the range of 4-15% by weight.

Optional composer In various embodiments, the polymer blend can optionally comprise one or more compatibilizers. In various embodiments, the optional compatibilizer may be one or more additional elastomeric components that are not crosslinked. For example, the polymer blend can include non-crosslinked elastomers selected from the group consisting of olefin elastomers, olefin multiblock interpolymers, and olefin block composites, such as those described above. The optional compatibilizer, if present, may be used in an amount ranging from 1 to 30% by weight, 2 to 20% by weight, or 3 to 10% by weight, based on the total weight of the polymer blend. ..

The compatibilizer may be any one or more of the above-mentioned elastomers in the form of non-crosslinking and non-crosslinking (eg, non-silane grafted, non-MAH grafted) form. In one or more embodiments, the compatibilizer may be an olefin block complex. Furthermore, in various embodiments, as described above, the compatibilizer may be an isotactic-polypropylene / ethylene-propylene olefin block complex.

Additives In various embodiments, hydrocarbon oils may also be included in the polymer blend. This additional component can reduce the subsequent diffusion and absorption of unwanted low molecular weight species typically found in fiber optic cable grease, thereby improving the balance between impact performance and gel compatibility.

When used, hydrocarbon oils are 0.2-10 parts / 100 parts resin (“phr”), or 0.3-3, based on 100 parts by weight of all polymer components present in the polymer blend. It may be present in the polymer blend in an amount in the range of 0 phr. Higher molecular weight hydrocarbon oils are preferred over low molecular weight hydrocarbon oils. In various embodiments, the hydrocarbon oil can have a viscosity greater than 400 centimeter stalk as measured by ASTM D-445. In addition, hydrocarbon oils can have a specific gravity of 0.86 to 0.90 as measured by ASTM D-1250. Hydrocarbon oils can also have a flash point above 300 ° C. as measured by ASTM D-92. In addition, hydrocarbon oils can have a pour point above −10 ° C. as measured by ASTM D-97. In addition, hydrocarbon oils can have an aniline point of 80-300 ° C. as measured by ASTM D-611.

In various embodiments, the polymer blend can include one or more fine particle fillers, such as glass fibers containing nanocomposites, various mineral fillers, and the like. Fillers, especially those with elongated or platelet-like particles that provide a higher aspect ratio (length / thickness), improve modulus and post-extrusion shrinkage properties. The filler may be included in the polymer blend in an amount in the range of 0.1-20 phr based on 100 parts by weight of all the polymer components present in the polymer blend.

The polymer blend may also contain other types of additives. Typical additives are antioxidants, co-crosslinkers, curing accelerators and scorch inhibitors, processing aids, coupling agents, UV stabilizers (including UV absorbers), antistatic agents, nucleating agents, Includes, but is not limited to, slip agents, lubricants, viscosity modifiers, tackifiers, antistatic agents, surfactants, extender oils, acid sweepers, flame retardants, and metal inactivating agents. These additives are typically used in conventional fashions, in conventional amounts, eg, 0.01 phr to 20 phr or more, based on 100 parts by weight of all polymer components present in the polymer blend. To.

Suitable UV stabilizers include hindered amine light stabilizers (“HALS”) and UV absorber (“UVA”) additives. Typical UVA additives are Ciba, Inc. Includes benzotriazole species such as Tinuvin 326 and Tinuvin 328 commercially available from. Blending of HAL and UVA additives is also effective.

Examples of antioxidants include hindered phenols such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydro-sinamate)] methane, bis [(β- (3,5-ditert-). Butyl-4-hydroxybenzyl) methylcarboxyethyl)]-sulfide, 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol) ), 2,2'-thiobis (4-methyl-6-tert-butylphenol), and thiodiethylenebis (3,5-di-tert-butyl-4-hydroxy) -hydrocinnamate, phosphite and phosphonite, eg. , Tris (2,4-di-tert-butylphenyl) phosphite and di-tert-butylphenyl-phosphonite, thio compounds such as dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipro. Pionate, various siloxanes, polymerization 2,2,4-trimethyl-1,2-dihydroquinoline, n, n'-bis (1,4-dimethylbenzyl-p-phenylenediamine), alkylated diphenylamine, 4,4 Included are'-bis (α, α-dimethylbenzyl) diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamine, and other hindered amine degradation inhibitors or stabilizers.

Examples of processing aids are metal salts of carboxylic acids such as zinc stearate or calcium stearate, fatty acids such as stearic acid, oleic acid, or erucic acid, stearic acid amides, oleic acid amides, erucic acid amides, or N, N. Fat amides such as'-ethylenebis-stearic acid amide, polyethylene wax, polyethylene oxide wax, ethylene oxide polymer, ethylene oxide and propylene oxide copolymer, vegetable wax, petroleum wax, nonionic surfactant, silicone solution, And polysiloxane, but are not limited to these.

Formulation In one or more embodiments, the components of the polymer blend used in the practice of the present invention can be added to a batch mixer or continuous mixer for melt blending. The ingredients may be added in any order, or one or more masterbatch may be prepared first for blending with other ingredients. Additives are usually blended with one or more other ingredients before being added to the bulk resin and / or filler. In one embodiment, the additive can be added directly to the formulation line without using a pre-prepared masterbatch. Typically, the melt blend is performed at a temperature above the maximum melting point of the molten polymer but below the activation temperature of the peroxide (if present). The melt-blended composition may then be fed to an extruder or injection molding machine to form into the desired article, or passed through a mold, or for storage, or It may be in pellets, tapes, strips, films, or any other shape to prepare the material for the next molding or processing. Optionally formed into pellets or some similar structure, the pellets and the like may then be coated with an anti-adhesive agent to facilitate handling during storage.

Formulation of the composition can be performed by standard equipment known to those of skill in the art. Examples of blending equipment are internal batch mixers such as Banbury ™ or Bolling ™ internal mixers. Alternatively, a single-screw or twin-screw mixer such as a Farrel ™ continuous mixer, a Werner and Pfreeider ™ twin-screw mixer, or a Buss ™ kneading continuous extruder can be used. The type of mixer used and the operating conditions of the mixer affect the properties of the composition such as viscosity, volume resistivity, and extruded surface smoothness.

Molded electrical articles containing the polymer blends of the present invention can be made by an injection molding process in which the compounded material is fed to an injection molding machine to produce molded parts of a given design.

As mentioned above, the cross-linked impact modified polymer can be cross-linked with other components of the polymer blend, including any desired cross-linking catalyst, after formulation, as described above. In various embodiments, such cross-linking steps may be carried out in pellets, granules, or other forms (ie, prior to molding into the final article) of the compound. In other embodiments, cross-linking of the impact modified polymer may be performed after the formation of optical cable protection components such as those described below.

For example, when a silane-functionalized elastomer is used as a crosslinkable impact-modified polymer, the elastomer can be crosslinked under ambient conditions known in the art. Although not required, the polymer blend, extruded blend, or optical cable component may be exposed to high temperature and / or external moisture, if desired. When high temperatures are used, the high temperatures are typically between the ambient and a temperature that can be 50 ° C., or even higher, for a period of time such that the impact-modified polymer reaches the desired degree of cross-linking. .. As in another example, when the MAH functionalized elastomer is used as a crosslinkable impact modified polymer, the impact modified polymer may be crosslinked at the high temperatures used during extrusion of the polymer blend.

Fiber Optic Cables In various embodiments, fiber optic cables can be prepared that include at least one extruded optical protection component made from the polymer blends described herein and incorporate at least one fiber optic transmission medium.

A cross-sectional view of the design of a typical loose buffer tube fiber optic cable is shown in FIG. In the design of the optical fiber cable 1, the buffer tube 2 is positioned radially around the central strength member 4 while spirally rotating in the axial length with respect to the tube. The spiral rotation allows the cable to bend without significantly extending the tube or fiber optic 6.

If a small number of buffer tubes are required, the foam filler rod 10 can be used as a low cost spacer that occupies the position of one or more buffer tubes to maintain the cable shape. The cable jacket 14 is generally manufactured from a polyethylene-based material.

The buffer tube is typically filled with optical cable grease or gel. Various gel compounds are commercially available, and most of them are hydrocarbon greases incorporating hydrocarbon oils. Others are polymer based and use low viscosity polymers that are formulated with hydrocarbon oils and other additives for even lower viscosities to facilitate filling. These greases and gels provide the floating and protection required for the direct environment surrounding the fiber, including eliminating voids. This filling compound (also referred to as "gel" or "grease") provides a barrier to water penetration that is detrimental to optical transmission performance.

In either oil-based grease or polymer formulated with the oil for lower viscosity, the hydrocarbon oil is typically a low molecular weight hydrocarbon oil and may be absorbed into the polymer buffer tube. Absorption typically has a detrimental effect on the mechanical properties of the tube, such as flexural modulus and pressure breakdown. The reduced breakdown voltage makes the fiber optics more susceptible to mechanical stress, thereby allowing increased signal attenuation and increasing the likelihood of catastrophic failure. Therefore, in addition to the minimum oil absorption value commonly referred to as "grease compatibility", good retention of modulus and breakdown resistance is a polymer used to make extruded optical protection components. It is an important performance characteristic of the material.

Many other buffer cable designs are possible. The use of central strength and tensile member size and construction material, buffer tube dimensions and number, metal exterior and multi-layer jacket material is included in the design elements.

A cross-sectional view of a typical core tube fiber optic cable, also known as a "central tube", is illustrated in FIG. The bundle 24 of the optical fiber 22 is positioned near the center of the optical cable 20 in the central columnar core tube 28. The bundle is embedded in the filling material 26. The waterproof tape 32 surrounds the ripcord 30 on the surface of the core tube. A corrugated coated steel cylinder 34 surrounds the tape to protect the bundle. The wire strength member 36 provides strength and rigidity to the cable. The jacket 38, generally made of a polyethylene-based material, surrounds all components. In this design, mechanical functions are incorporated into an outer sheath system consisting of core tubes, polyolefin jacket layers, tensile and compressive strength members, metal exteriors, core wraps, water blocking components, and other components.

Core tubes are typically smaller in diameter than buffer tubes to accommodate the use of bundles of fibers, or ribbon components, including optical fibers. Color-coded ties are typically used to bundle and identify the fibers. The core tube contains a waterproof grease or superabsorbent polymer element that surrounds the fiber optic component. Optimal material properties for core tube components are often similar to those for buffer tube applications.

A cross-sectional view of a typical slotted core cable design is shown in FIG. The fiber optic cable 30 includes a jacket 48 and a slotted core 32 having a central member 34. The central member prevents buckling and controls the axial shrinkage of the profile shape of the core with extrusion slots. Jackets and slotted cores are typically made from polyolefin-based materials.

The slotted core has a slot 36 in which the optical fiber 38 is located. The filler rod 40 may also occupy one or more slots. The waterproof layer 42, which may have one or more ripcords 44, surrounds the slotted core 32. The dielectric strength member layer 46 surrounds the waterproof layer.

Fiber optic cables such as those described above can typically be made in a series of sequential manufacturing steps. Optical transmission fibers are generally manufactured in the early stages. The fiber can have a polymer coating for mechanical protection. These fibers can be assembled into bundled or ribbon cable configurations or incorporated directly into the manufacture of the cable.

Optical protection components can be manufactured using an extrusion manufacturing process. Typically, a uniaxial plastic extruder dispenses the polymer melted and mixed under pressure to a wire and cable crosshead. The crosshead changes the melt flow perpendicular to the extruder and forms the flow into melt components. For buffers and core tubes, one or more fiber optic or fiber assemblies and greases are fed to the back of the crosshead, exit the crosshead within the fusion tube, and then cooled and solidified in a water trough system. This component is finally recovered as the final component on the take-up reel.

To produce a component consisting of two or more layers of material, there is typically a separate plastic extruder that feeds the molten components to the multilayer crosshead, where it is molded into the desired multilayer construction.

Slotted core tubes and other profile extrusion components are typically extruded in a similar profile extrusion process incorporating suitable molding dies, followed by fiber optic components to manufacture the final cable. Combined with.

Tension systems are used to feed the fiber components to the tube manufacturing process to control the extra fiber length. In addition, component selection, tube extrusion, and crosshead equipment, as well as machining conditions, are optimized to provide the final component where post-extrusion shrinkage does not result in excessive loosening of the fiber optic component.

Extruded optical protection components, along with other components such as core components, exteriors, wraps, etc., are machined in one or more steps to produce the final cable construction. This typically involves processing on a cable production line where the components are assembled by a manufacturing extruder / crosshead and then used to apply a polymer jacket.

Test method Embrittlement temperature The embrittlement temperature is determined according to ASTM D746.

Density Density is determined according to ASTM D792.

Flexural Modulus The flexural modulus is determined according to ASTM D790.

Bending stress at 3.5% strain The bending stress is determined according to ASTM D790.

Izod impact strength Determine the notched Izod impact strength according to ASTM D256.

Melt Index The Melt Index, or I _2, is measured according to ASTM D1238 at 190 ° C./2.16 kg and is reported in grams elution per 10 minutes.

Molecular Weight Distribution The gel permeation chromatography (“GPC”) system consists of a Polymer Char GPC-IR High Temperature Chromatograph equipped with an IR4 infrared detector from Polymer ChAR (Valencia, Spain). Data collection and processing is done using Polymer Char software. The system is also equipped with an online solvent degassing device.

Suitable high temperature GPC columns such as four 30 cm long Shodex HT803 13 micron columns or four 30 cm Polymer Labs columns filled with a 13 micron mixed pore size (Olexis LS, Polymer Labs) can be used. The sample rotation compartment is operated at 140 ° C. and the column compartment is operated at 150 ° C. Samples are prepared at a concentration of 0.1 grams of polymer in 50 ml of solvent. The chromatography solvent and sample preparation solvent are 1,2,4-trichlorobenzene (“TCB”) containing 200 ppm of 2,6-di-tert-butyl-4-methylphenol (“BHT”). Spurge the solvent with nitrogen. The polymer sample is stirred at 160 ° C. for 4 hours. The injection volume is 200 microliters. The flow velocity through the GPC is set to 1 mL / min.

The GPC column set is calibrated by running 21 narrow molecular weight distribution polystyrene standards. The molecular weight of the standard (“MW”) ranges from 580 g / mol to 8,400,000 g / mol, and the standard is contained in the six “cocktail” mixtures. Each standard mixture has at least 10 gaps between the individual molecular weights. The standard mixture is purchased from Polymer Laboratories. The polystyrene standard is 0.025 g in a 50 mL solvent for a molecular weight of 1,000,000 g / mol or more and 0.05 g in a 50 mL solvent for a molecular weight of less than 1,000,000 g / mol. Prepare. The polystyrene standard is dissolved at 80 ° C. with stirring for 30 minutes. To minimize degradation, a narrowly distributed standard mixture is run first and in ascending order of maximum molecular weight components. Williams and Ward, J. Mol. Polym. Sci. , Polym. The peak molecular weight of the polystyrene standard was converted to the molecular weight of polyethylene using equation (1) as described in Letters, 6, 621 (1968):
M polyethylene = Ax (M polystyrene) B (equation 1)
In the formula, M is the molecular weight of polyethylene or polystyrene (the molecular weight described) and B is equal to 1.0. It is known to those skilled in the art that A may be in the range of about 0.38 to about 0.44 and will be determined at the time of calibration using a widely distributed polyethylene standard. The use of this polyethylene calibration method to obtain molecular weight values such as molecular weight distribution (MWD or M _w / M _n ) and associated statistics is defined herein as a modification of Williams and Ward. The number average molecular weight, the weight average molecular weight, and the z-average molecular weight are calculated from the following equations.

Tensile modulus (secant line 1%)
The tensile modulus is determined according to ASTM D638.

Tensile strength Determine the tensile strength according to ASTM D638.

Tensile Elongation Determines tensile elongation according to ASTM D638.

Weight increase (grease resistance)
Weight gain is determined according to YD / T1118.1-2001.
1.6 Tensile test pieces (ASTM D638 I type) are selected, and the mass of each test piece is measured and indicated by _mfresh .
2. 2. Grease the tensile test piece.
a. First, the gel is degassed in a vacuum oven at 80 ° C. to eliminate any air bubbles or air pockets in the grease.
b. Carefully coat only one side of the test piece with grease using a blade to a grease thickness of less than 1 mm.
c. The coated test piece is then placed on the plate with the grease side up.
3. 3. Aging in the oven: The plate containing the specimen is then placed in an air-circulated oven for aging. The aging condition is 360 hours at 80 ° C.
4. After aging, weigh the tensile test piece: After aging, remove the test piece from the oven, wipe it with tissue paper, cool to room temperature, and adjust until measurement for 24 hours. The mass of the _aged tensile test piece is indicated by _maging , and the weight increase is calculated according to the following equation:

Materials The following materials are used in the following examples.

Polybutylene terephthalate used ( "PBT") has a 1.3 g / cm ³ density and ^9cm 3/10 min melt volume flow rate (MVR) at 250 ° C. and 2.16kg, BASF Chemical Company SE, Ludwigshafen , Ultradur B6550 LN available from Germany.

Crystalline polypropylene used is a Globalene PC366-5 having 55.3% crystallinity, a density of 0.903 g / cm ^3, and a melt index of 5.5 g / 10 min at 230 ° C. / 2.16 kg .. PC366-5 is commercially available from LCY Chemical Corporation (Taipei, Taiwan).

Silane-grafted polyolefin Elastomers are a blend of silane-grafted ENGAGE ™ 8200 and ENGAGE ™ 8402 Polyolefin Elastomers, both from The Dow Chemical Company, Midland, Michigan, USA. It is available. The elastomer blend comprises 59 weight percent ENGAGE ™ 8200 and 38 weight percent ENGAGE ™ 8402 based on the total weight of the silane grafted polyolefin elastomer. ENGAGE ™ 8200 is an ethylene / octene polyolefin elastomer having a melt index in the range of 4.0-6.0 g / 10 min and a density in the range of 0.867-0.873 g / cm ³ . ENGAGE ™ 8402 is an ethylene / octene polyolefin elastomer having a melt index in the range of 22.5 to 37.5 g / 10 min and a density in the range of 0.899 to 0.905 g / cm ³ . Silane-grafted polyolefin elastomers have a melt index in the range of 5.0-8.0 g / 10 min, a maximum water content of 20 ppm, and 1.40 to 1.90 wt% silane monomer (determined by FTIR). Has a content.

Silane-grafted polyolefin elastomer blends at the reactive extrusion step, 250 rpm, 20 kg / hour throughput rate, and temperature profiles starting from the feed barrel to the mold, 100 ° C / 190 ° C / 230 ° C / 230. Vinyl trimethoxysilane (VTMS) on a 27 mm 48 L / D co-rotating elastomer twin-screw extruder operating at ° C./230 ° C./230 ° C./230 ° C./230 ° C./190 ° C./190 ° C./190 ° C./190 ° C. ) And a peroxide to prepare it. The grafting temperature is set to 230 ° C. The degree of vacuum is set to 0.08 MPa. The VTMS filling level is 2% by weight and the peroxide (Luperox 101) filling level is 0.1% by weight. VTMS and peroxide are mixed well before being injected into the extruder. The grafting level of the polyolefin elastomer is 1.62% by weight.

The olefin multiblock interpolymer is an ethylene / octene interpolymer and has a target density of 0.870 g / cm ³ and a target melt index of 0.5 g / 10 min. Ethylene / octene multiblock interpolymers are prepared according to the procedures detailed in Example numbers 24-28 and 29-40 in US Pat. No. 7,947,793. The ethylene / octene multiblock interpolymer has the following properties.
Density: 0.873 g / cm ³
I _2: 0.57g / 10 minutes I _10: 6.06g / ₁₀ min _{I 10} / I 2: 10.63
Weight average molecular weight (“M _w ”) (g / mol): 148,600
Number average molecular weight (“M _n ”) (g / mol): 53,590
Multivariance index (“M _w / M _n ”): 2.77
Heat of fusion (J / g): 38.23
Melting temperature (“T _m ”): 118.4 ° C
Crystallization temperature ( _{"T c"):} 92.0 ℃
Overall octene content (mol%): 18.9
Octene content in soft segment (mol%): 27.1
Octene content (mol%) in hard segment: 1.4
ΔOcene: 25.7

The silane grafted olefin multiblock interpolymer is the same as the ethylene / octene interpolymer, as described immediately before, but is grafted with a silane functional group. The silane monomer content of the silane grafted ethylene / octene interpolymer is 1.62% by weight. The silane grafted ethylene / octene interpolymer has substantially the same density as the ungrafted ethylene / octene interpolymer.

Silane-grafted ethylene / octene multiblock interpolymers are prepared in a 27 mm twin-screw extruder at a melt compounding temperature of 230 ° C. VTMS was added in 2% by weight in the presence of 1,000 ppm (0.1%) of Luperox 101 peroxide.

DFDA-5480 has a density of about 0.927 g / cm ³ and a melt index of about 3.05 g / 10 min, 1.7% by weight of tin catalyst, 3.5% by weight of oxidation. A polyethylene / catalyst masterbatch containing an inhibitor and an amount of 1.67% by weight of the metal inactivating agent. DFDA-5480 is commercially available from The Dow Chemical Company (Midland, Michigan, USA).

DHT-4A has the chemical formula Mg ₁ − _x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (0 <x ≦ 5).
It is an acid sweeping agent having, and is described as aluminum hydroxide magnesium carbonate hydrate. HDT-4A is described in Kisuma Chemicals B. et al. V. It is commercially available from (Netherlands).

NA-11A is a sodium 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate (CAS NO.85209-) commercially available from ADEKA Corporation (Tokyo, Japan). It is a nucleating agent which is a nucleating agent having 91-2).

IRGANOX ™ 1010 has the chemical name pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) commercially available from BASF SE (Ludwigshafen, Germany). It is an antioxidant.

IRGANOX ™ 168 is an antioxidant commercially available from BASF SE (Ludwigshafen, Germany) with the chemical name tris phosphite (2,4-ditert-butylphenyl).

BC B is an isotactic-polypropylene / ethylene-propylene olefin block composite having a density of 0.905 g / cm ³ and a melt index of 6 at 230 ° C.

BC B is prepared according to the following procedure. Catalyst-1 ([[rel-2', 2'''-[(1R, 2R) -1,2-cyclohexanediylbis (methyleneoxy-κO)]] bis [3- (9H-carbazole-9-yl)) -5-Methyl [1,1'-biphenyl] -2-olato-κO]] (2-)] dimethyl-hafnium), and cocatalyst-1, tetrakis (pentafluorophenyl) volley methyldi (C _14-18) A mixture of (alkyl) ammonium salts (substantially Armeen ™ available from Akzo-Nobel, Inc., as disclosed in Example 2 of US Pat. No. 5,919,983). M2HT), HCl, and Li [prepared by the reaction of B (C ₆ F ₅ ) ₄ ]) are purchased from Boulder Scientific and used without further purification.

CSA-1 (diethylzinc or DEZ) and cocatalyst-2 (modified methylarmoxane (“MMAO”)) are purchased from Akzo Nobel and used without further purification. The solvent for the polymerization reaction is a hydrocarbon mixture (ISPAR® E) available from ExxonMobil Chemical Company and is purified through a 13X molecular sieving bed prior to use.

The block complex is prepared using two continuously stirred tank reactors (“CSTR”) connected in series. The volume of the first reactor is about 12 gallons and the volume of the second reactor is about 26 gallons. Each reactor is filled with fluid and set to operate under steady state conditions. The monomer, solvent, hydrogen, catalyst-1, cocatalyst-1, cocatalyst-2, and CSA-1 are fed to the first reactor according to the process conditions outlined in Table 1. The contents of the first reactor listed in Table 1 flow into a second reactor in series. Additional monomers, solvents, hydrogen, catalyst-1, cocatalyst-1, and optionally cocatalyst-2 are added to the second reactor.

The block complex prepared as described above has the following properties shown in Table 2.

Example 1 (comparison)
Five comparative samples [CS1-CS5] are prepared using the formulations provided in Table 3 below. It is used as it receives the PBT in CS1. Comparative samples CS2-CS5 with throughput rates of 600 rpm and 12 kg / hour, and a temperature profile starting from the feed barrel to the mold, 100 ° C / 130 ° C / 200 ° C / 200 ° C / 200 ° C / 200 ° C. Prepared by blending and extruding components on an 18 mm 48 L / D twin-screw extruder operating at / 200 ° C.

Comparative samples CS1-CS5 are analyzed according to the test method described above. The results are provided in Table 4 below.

Example 2
Two samples (S1 and S2) are prepared using the formulations shown in Table 5 below. Samples S1 and S2 are prepared according to the procedure described in Example 1 above.

Samples S1 and S2 are analyzed according to the test method described above. The results are provided in Table 6 below.

As can be seen from the results in Table 6, the crosslinked impact modified polymer provides superior grease resistance specifically compared to the corresponding non-crosslinked comparative sample CS5, while compared to conventional materials such as CS1 and CS2. It also maintains improved impact strength and embrittlement temperature.

Reference example 3
Six samples (S3 to S8) are prepared using the formulations shown in Table 7 below. Samples S3 to S8 are prepared according to the procedure described in Example 1 above.

Samples S3 to S8 are analyzed according to the test method described above. The results are provided in Table 8 below.

As can be seen from the results in Table 8, the crosslinked impact modified polymer has a lower concentration than the corresponding non-crosslinked comparative sample CS5, even without the use of a diblock compatibilizer as in Example 2. Provides excellent grease resistance. In addition, the samples S3 to S8 also maintained improved impact strength and embrittlement temperature as compared to conventional materials such as CS1 and CS2. However, at higher concentrations of impact modified polymer (25-50% by weight), reduced tensile and flexural moduli are observed.

Example 4
Three samples (S9-S11) are prepared using the formulations shown in Table 9 below. Samples S9 to S11 are prepared according to the procedure described in Example 1 above.

Samples S9 to S11 are analyzed according to the test method described above. The results are provided in Table 10 below.

As can be seen from the results in Table 10, the crosslinked impact modified polymers provide superior grease resistance, especially compared to the corresponding non-crosslinked comparative sample CS4 (comparing S9 with S4), while CS1 and CS2. It also maintains improved impact strength and embrittlement temperature compared to conventional materials such as. However, at higher concentrations of impact modified polymer (25% by weight), reduced tensile and flexural moduli are observed.

Example 5
Two samples (S12 and S13) are prepared using the formulations shown in Table 11 below. Samples S12 and S13 are prepared according to the procedure described in Example 1 above.

Samples S12 and S13 are analyzed according to the test method described above. The results are provided in Table 12 below.

As can be seen from the results in Table 12, crosslinked impact modified polymers provide improved impact strength and embrittlement temperature compared to conventional materials such as CS1 and CS2. S12 and S13 further provide comparable grease resistance without the use of diblock compatibilizers as in Example 4. However, at higher concentrations of impact modified polymer (25% by weight), reduced tensile and flexural moduli are observed.
It should be added that the present invention includes the following aspects.
[1]
Extruded optical cable protection component
(A) Crystalline polypropylene with a crystallinity of at least 55 percent,
(B) Containing extruded polymer blends, including crosslinked impact modified polymers.
The extruded optical cable protection component, wherein the crosslinked impact modified polymer is an elastomer selected from the group consisting of a crosslinked silane functionalized elastomer, a crosslinked maleic anhydride functionalized elastomer, or a combination thereof.
[2]
The crystalline polypropylene is present in an amount in the range of 45-95 weight percent based on the total weight of the polymer blend and the crosslinked impact modified polymer is 4-50 weight percent based on the total weight of the polymer blend. The extruded optical cable protection component according to [1], which is present in an amount in the range of.
[3]
The elastomer of the crosslinked impact modified polymer is selected from the group consisting of polyolefin elastomers, olefin multiblock interpolymers, olefin block composites, and combinations of two or more of them, [1] or [2]. The extruded optical cable protection component according to any one of.
[4]
Further comprising a non-crosslinked elastomer component selected from the group consisting of olefin elastomers, non-olefin elastomers, olefin multiblock interpolymers, olefin block composites, and mixtures of two or more of them [1]-[3]. The extruded optical cable protection component according to any one of the above.
[5]
The extruded optical cable protection component according to any one of [1] to [4], wherein the polymer blend has a weight gain of less than 10 percent in LT-410A after 16 days.
[6]
The polypropylene has a melt flow index (I2) in the range of 1-20 grams / 10 minutes (eluting) and the polymer blend is notched at least 100 joules / meter (“J / m”) at 23 ° C. The above-mentioned item according to any one of [1] to [5], which has an isot impact strength and the polymer blend has a 1% split line coefficient of at least 1,200 megapascals (“MPa”) at 23 ° C. Extruded optical cable protection component.
[7]
Further comprising one or more additional components selected from the group consisting of antioxidants, stabilizers, nucleating agents, acid sweeping agents, fillers, and combinations of two or more of them [1] to. The extruded optical cable protection component according to any one of [6].
[8]
It is an optical fiber cable
(A) The extruded optical fiber cable protection component according to any one of [1] to [7].
(B) The optical fiber cable comprising at least one optical fiber transmission medium.
[9]
It ’s a polymer blend,
(A) Crystalline polypropylene with a crystallinity of at least about 55 percent,
(B) Impact-modified polymers selected from the group consisting of silane-grafted polyolefin elastomers, silane-grafted olefin multi-block interpolymers, silane-grafted olefin block composites, and combinations of two or more of them.
(C) Non-silane grafted elastomers selected from the group consisting of olefin multiblock interpolymers, olefin block composites, and combinations thereof.
(D) The polymer blend comprising, and a condensation catalyst.
[10]
The crystalline polypropylene is present in the polymer blend in an amount in the range of 50-90% by weight based on the total weight of the polymer blend, and the impact modified polymer is the total of the polymer blend in the polymer blend. It is present in an amount in the range of 4 to 45% by weight based on weight, and the non-silane grafted compatibilizer is in an amount in the polymer blend in the range of 1 to 10% by weight based on the total weight of the polymer blend. The polymer blend according to [9], wherein the condensation catalyst is present in the polymer blend in an amount in the range of 0.01 to 0.5% by weight based on the total weight of the polymer blend.

Claims (1)

A polymer blend, based on the total weight of the polymer blend.
(A) 55-90% by weight of crystalline polypropylene having a crystallinity of at least 55%.
(B) 4 to 30 % by weight of the impact modified polymer selected from the group consisting of silane grafted ethylene / octene polyolefin elastomers and silane grafted ethylene / octene multiblock interpolymers.
(C) 1 to 10% by weight of isotactic-polypropylene / ethylene-propylene olefin block composite, and (d) 0.01 to 0.5% by weight of condensation catalyst.
The polymer blend containing.