1. Field of the Invention
This invention relates to the field of polymers and more specifically to the field of film products comprising metallocene catalyzed polypropylene.
2. Background of the Invention
Polypropylene is typically produced in continuous polymerization reactors that may include loop reactors. A monomer stream may be introduced into the loop reactor and then circulated with an appropriate catalyst to produce the polypropylene. Ziegler-Natta catalysts have been the conventional catalysts used to produce polypropylene by polymerization. After polymerization, the polypropylene may typically be withdrawn from the reactor in powder or granular form. The granular polymer may then be subjected to appropriate purification and processing steps. After such steps, the polymer may be extruded in a melted state through an extruder and die mechanism to convert the polymer to a film or other product. Such film products may then be used to produce end-use products such as slit tapes, woven fabrics, and the like.
The conventional processes for producing such end-use products, for instance woven fabrics, may include exposing the film products to high stress operations such that the end-use products have reduced strength and toughness properties. Therefore, there is a need for a film product that comprises high strength and toughness properties. A further need exists for a film product that substantially retains its strength and toughness properties after exposure to the high stress operations used to convert it to a desired end use product.
One embodiment of the present invention is a film product comprising a metallocene catalyzed polypropylene, and a tenacity of at least about 2.5 g/den, wherein the film product is capable of being drawn at a draw ratio of from about 5.0:1 to about 10.0:1. The film product can further have a tenacity of about 5.0 g/den and capable of being processed into at least one of a slit tape and a woven product. The film product and/or the slit tape product can be capable of being woven into a woven product. The metallocene catalyzed polypropylene can be a metallocene catalyzed isotactic polypropylene.
Another embodiment of the invention can be a film product of a process comprising: polymerizing a monomer in the presence of a metallocene catalyst system to produce metallocene catalyzed polypropylene, wherein the metallocene catalyst system comprises a metallocene catalyst; processing the metallocene catalyzed polypropylene into a film product; and drawing the film product at a draw ratio of from about 5.0:1 to about 10.0:1, the film product comprising a tenacity of at least about 2.5 g/den. The monomer can bed a propylene and the metallocene catalyst system can include a co-catalyst, such as an organoaluminum compound. The metallocene catalyst system can include at least one of a homogenous catalyst system and a supported catalyst system. The polymerizing of the monomer can be performed in a loop reactor system. The process can further include extruding the metallocene catalyzed polypropylene and drawing the metallocene catalyzed polypropylene through a die. The process can further include processing the film product into a slit tape product, such as by slitting the film product and/or weaving the slit tape product into a fabric and/or weaving the film product into a fabric. The film product can be a metallocene catalyzed isotactic polypropylene, such as having an isotacticity of less than about 99.0 percent.
Yet another embodiment of the invention is a method of producing a metallocene catalyzed polypropylene film product having a tenacity of at least about 2.5 g/den, the method comprising: extruding a metallocene catalyzed polypropylene, forming the metallocene catalyzed polypropylene into a substantially flat product, cooling the substantially flat product, and stretching the substantially flat product into the metallocene catalyzed polypropylene film product. The formation can include using a die to form the substantially flat product. The cooling can include cooling the substantially flat product with cooling equipment, the cooling equipment selected from the group consisting of: (i) at least one chill roller; and (ii) at least one quench bath. The at least one chill roller can cool the substantially flat product to a temperature of from about 30 degrees centigrade to about 60 degrees centigrade. The stretching can further include: (i) heating the substantially flat product; (ii) drawing the substantially flat product; and (iii) annealing the substantially flat product. The heating can further include heating the substantially flat product to a temperature of from about 130 degrees centigrade to about 180 degrees centigrade. The drawing can further include drawing the substantially flat product at a draw ratio of from about 5.0:1 to about 10.0:1. The annealing can further include heating the substantially flat product to a temperature of from about 130 degrees centigrade to about 170 degrees centigrade. The method can further include processing the film product into a slit tape product, weaving the slit tape product into a woven product, and weaving the film product into a woven product.
A further embodiment of the invention is a method of weaving a woven product from a slit tape having a tenacity of at least about 2.5 g/den, wherein the slit tape comprises a processed metallocene catalyzed polypropylene film product, the method comprising: supplying the slit tape to a loom, the slit tape being configured to be stored in a loom beam; and weaving the slit tape into the woven product, the woven product having a tenacity of within about 10.0 percent of the tenacity of the slit tape. The method can include the weaving a plurality of fill yarns into the woven product. The woven product can have a tenacity of within about 10.0 percent of the tenacity of the metallocene catalyzed polypropylene film product.
The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:
As seen in
The following describes an exemplary application of the reactor system 5 as illustrated on
In alternative embodiments, the m-iPP may be treated with additives. The additives may be added to the reactor system 5 during the polymerization. Alternatively, the additives may be added to the m-iPP after polymerization. The additives may comprise less than about 4.0 weight percent of the m-iPP. The use of additives for polymers is well known in the art. Suitable additives may include but are not limited to antioxidants, process stabilizers, light stabilizers, acid scavengers, lubricants, processing aids, anti-blocking additives, slip additives, antifogging additives, antistatic additives, flame retardants, nucleating agents, fillers, pigments and antimicrobial agents.
Catalyst systems useful in the formation of isotactic polyolefins include the racemic bis-indenyl compounds of the type disclosed in U.S. Pat. No. 4,794,096 to Ewen. The bis(indenyl) ligand structures may be unsubstituted or they may be substituted as described below. Examples of bis(indenyl) type catalysts that can be used include: rac-dimethylsilylanediylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride and rac-dimethylsilylanediylbis (2-methyl-1-indenyl)zirconium dichloride.
Other isospecific metallocenes useful in carrying out the invention can be based upon cyclopentadienyl fluorenyl ligand configurations which are substituted to provide a lack of bilateral symmetry. Catalysts of this nature are disclosed in U.S. Pat. No. 5,416,228 to Ewen et al. Here, the ligand structure is configured so that one cyclopentadienyl group of a bridged ligand has a bulky group on one and only one of the distal positions of a cyclopentadienyl ring. Typical of such metallocenes is isopropylidene (3-tertiary butyl cyclopentadienyl fluorenyl) zirconium dichloride.
Other isospecific metallocenes that can be used in the present invention are based on cyclopentadienyl fluorenyl ligand structures as disclosed in U.S. Pat. No. 6,559,089 to Razavi et al. The ligand structures are characterized by bridged cyclopentadienyl and fluorenyl groups in which the cyclopentadienyl group is substituted at both proximal and distal positions. The distal substituent is desirably a bulky group such as a tertiary butyl group, and the proximal substituent is desirably a less bulky group such as a methyl group which may be either vicinal or non-vicinal to the distal substituent. The fluorenyl group may be substituted or unsubstituted with up to eight substituent groups but desirably is unsubstituted at the positions which are distal to the bridgehead carbon atom. Specifically disclosed in U.S. Pat. No. 6,559,089 are isopropylidene(3-tertiary butyl, 5-methyl cyclopentadienyl fluorenyl) zirconium dichloride and isopropylidene(3-tertiary butyl, 2-methyl cyclopentadienyl fluorenyl) zirconium dichloride.
Yet other isospecific metallocenes based upon bis(fluorenyl) ligand structures are disclosed in U.S. Pat. No. 5,945,365 to Reddy. Here, the ligand structure is characterized by two bridged fluorenyl groups with 1 or 2 substituents at distal positions on each fluorenyl group with one group of substituents being located transversely from the other with respect to a plane of bilateral symmetry extending through the bridge group. Desirable ligand structures are bridged bisfluorenyl ligands substituted at the 4,4′ positions by methyl, methoxy, isopropyl or tertiary butyl groups. For a further description of isospecific metallocenes, reference is made to the aforementioned U.S. Pat. 4,794,096, 5,416,228 and 5,945,365 and 6,559,089, the entire disclosures of which are incorporated herein by reference.
Catalysts that produce isotactic polyolefins are disclosed in U.S. Pat. Nos. 4,794,096 and 4,975,403 to Ewen. These patents disclose stereorigid metallocene catalysts that polymerize olefins to form isotactic polymers and are especially useful in the polymerization of highly isotactic polypropylene. As disclosed, for example, in the aforementioned U.S. Pat. No. 4,794,096, stereorigidity in a metallocene ligand is imparted by means of a structural bridge extending between cyclopentadienyl groups. Specifically disclosed in this patent are stereoregular hafnium metallocenes that may be characterized by the following formula:
R″(C5(R′)4)2HfQp (5)
In Formula (5), (C5(R′)4) is a cyclopentadienyl or substituted cyclopentadienyl group, R′ is independently hydrogen or a hydrocarbyl radical having 1-20 carbon atoms, and R″ is a structural bridge extending between the cyclopentadienyl rings. Q is a halogen or a hydrocarbon radical, such as an alkyl, aryl, alkenyl, alkylaryl, or arylalkyl, having 1-20 carbon atoms, and p is 2.
The metallocene polypropylene product of loop reactor 5 may comprise a generally isotactic stereoregularity (m-iPP). Alternatively, the polypropylene product may comprise a generally syndiotactic stereoregularity (m-sPP). The isotacticity of the polypropylene product may be measured in terms of the percentage content of meso configurations in an amount of polypropylene product. For instance, the isotacticity of the m-iPP may have an isotacticity of less than about 99.0 percent by weight of the m-iPP. Alternatively, the m-iPP may have an isotacticity of less than about 95.0 percent by weight of the m-iPP. Further alternatives comprise the m-iPP having less than about 90.0 percent isotacticity by weight of the m-iPP. The m-iPP may also comprise a regioregularity having 1,2 insertions and 2,1 insertions, which are represented in terms of insertion errors. The insertion errors may be measured in terms of the percent occurrence of the 2,1 insertions in relation to the 1,2 insertions. For instance, the m-iPP may have insertion errors of more than about 5.0 percent by weight of the m-iPP. Alternatively, the m-iPP may have insertion errors of more than about 2.0 percent by weight of the m-iPP. Further alternatives comprise the m-iPP having insertion errors of less than about 0.5 percent by weight of the m-iPP. Other properties of the m-iPP comprise a melting temperature of from about 125° C to about 165° C. In addition, the m-iPP may have a melt flow rate (“MFR”) of from about 2.0 dg/min to about 10.0 dg/min, as measured per ASTM D1238 “L”. Further properties include the m-iPP having a molecular weight distribution (“MWD”) of from about 2.0 to about 7.0.
Processing polypropylene into a film product that may be slit into tape is well known in the art. In an embodiment shown in
The following describes an exemplary application of the embodiment as illustrated on
In the lateral stretching section 90 of
In an alternative embodiment shown in
The following describes an exemplary application of the embodiment as illustrated on
In the lateral stretching section 90 of
The following describes an exemplary illustrative embodiment of the weaving process 175 depicted in
To further illustrate various illustrative embodiments of the present invention, the following examples are provided.
In this example, m-iPP and zn-iPP polymers were produced, and the stereoregularity and regioregularity of these polymers were compared. TABLE 1 illustrates the stereoregularity and regioregularity of the m-iPP over the Ziegler-Natta catalyzed polypropylene (“zn-iPP”). In this example, the stereoregularity in terms of isotacticity and regioregularity in terms of the insertion errors of the m-iPP and zn-iPP were measured by Nuclear Magnetic Resonance (“NMR”). Table 1 represents the average resulting isotacticity and insertion errors of such measurements. As shown in TABLE 1, the m-iPP measurements indicate about a 15 percent lower isotacticity than the zn-iPP measurements. In addition, the insertion errors may be more than twice as prevalent in the m-iPP measurements than in the zn-iPP measurements. Consequently, such higher levels of chain deformities may result in a m-iPP film product that produces a stronger woven product than a woven product produced from the zn-iPP film product.
In this example, m-iPP and zn-iPP polymers were produced, and slit tapes were then produced from film products made of these polymers. For the production of the m-iPP and the zn-iPP polymers, a propylene monomer was polymerized by methods typical to the art. In addition, a similar additive package was added to both the m-iPP and the zn-iPP prior to pellitization.
Table 2 represents MFR and MWD values typical of the polymers referred to in this example. As illustrated in TABLE 2, the m-iPP polymer exhibited an average MFR and MWD lower than did the zn-iPP polymer.
TABLE 3 represents average properties of each slit tape made from the film products that were produced from the m-iPP and zn-iPP polymers. The polymers were processed at the limits of their drawability at their respective run conditions, that is they processed with an acceptable and similar level of draw breaks. The draw ratios used for the miPP and the zniPP were each close to the maximum. These average properties were determined by taking 5-10 measurements of each property using the procedures set forth previously.
As TABLE 3 illustrates, the m-iPP and zn-iPP slit tapes had similar deniers. However, the m-iPP slit tape exhibited a higher modulus and lower tape elongation than the zn-iPP slit tape. As further illustrated, the m-iPP tapes exhibited maximum tenacity at a draw ratio higher than the zn-PP tapes. As further illustrated, the m-iPP slit tape exhibited about a 16 percent higher tape tenacity, before weaving, than the zn-iPP slit tape. In addition, the m-iPP slit tape exhibited about a 4 percent drop in tape tenacity after weaving (tape unwoven and removed for measurement), and the zn-iPP slit tape exhibited about a 42 percent drop in tape tenacity after weaving. From the results shown in TABLES 2 and 3, the m-iPP slit tapes have a higher strength than the zn-iPP slit tapes, both before and after weaving. In addition, the m-iPP slit tapes may withstand the stresses of weaving better than the zn-iPP slit tapes. Therefore, to produce a woven product with substantially similar toughness and strength properties, the m-iPP woven product may comprise less polymer than the zn-iPP produced woven product.
EXAMPLES 3-8 illustrate m-iPP slit tapes produced at varying draw ratios, and EXAMPLES 9-14 illustrate zn-iPP slit tapes produced at varying draw ratios. The m-iPP polymer used to produce the m-iPP slit tape exhibited a MFR of 4.0 g/10 minutes. The zn-iPP polymer used to produce the zn-iPP slit tape exhibited a MFR of 3.8 g/10 minutes.
The slit tapes were prepared from the m-iPP and zn-iPP polymers on a conventional Bouligny Tape Line having an extruder setting with temperature settings of about 200-210-220-230-240-250 C. In addition, the Bouligny Tape Line comprised a quench tank operating at about 27 degrees centigrade. The take away speed from the quench tank was a speed of at about 100 feet per minute. The film (or tapes) was heated in an oven set at about 200 C. In the drawing section, the film product was drawn at a draw ratio of about 5.0:1 to about 8.0:1. The drawn film product was annealed in the annealing section, which was run at a set temperature of about 160° C. The slit tapes illustrated in EXAMPLES 3-14 exhibited a denier of about 1000 grams/9000 meters. Various properties of the slit tapes produced at the varying draw ratios were measured, and the results are illustrated on TABLE 4, wherein Examples 3-8 are m-iPP and Examples 9-14 are zn-iPP.
From the results in TABLE 4, the m-iPP tapes exhibited statistically equal or better tenacity at draw ratios of 6.5:1 and higher, and better elongation at all draw ratios explored, that is at the same tenacity the m-iPP tapes display much improved elongation.
It will be understood that the present invention is not limited to the Tenter Frame and Bouligny Slit Tape processes but may comprise any suitable process for the production of the film product and slit tape. Moreover, the present invention is not limited to the loom in producing a woven product but may comprise any suitable process for the production of a woven product from a film product or slit tape. Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.