阅读说明：本技术 用于膜的聚丙烯 (Polypropylene for films ) 是由 S·P·施密特 C·A·斯波福德 G·J·派勒特 于 2019-09-25 设计创作，主要内容包括：本发明的公开内容提供具有高光泽和最小或没有雾度同时还具有高熔体强度(高耐温性)和相对高劲度的聚丙烯组合物。该聚丙烯组合物含有一种或多种基础聚丙烯(例如,被修剪的聚丙烯(tPP))和一种或多种澄清剂。该基础或被修剪的聚丙烯含有至少50mol％丙烯且具有范围为7至22的分子量分布(Mw/Mn),小于2,500,000g/mol的z-均分子量,至少0.95的支化指数(g′-(vis))和使用拉伸流变仪在190℃下测定的小于20cN的熔体强度。可由一种或多种高熔体强度聚丙烯(HMS PP)生产该基础或被修剪的聚丙烯。(The present disclosure provides compositions having high gloss and minimal or no shinePolypropylene compositions having haze while also having high melt strength (high temperature resistance) and relatively high stiffness. The polypropylene composition contains one or more base polypropylenes (e.g., a trimmed polypropylene (tPP)) and one or more clarifying agents. The base or trimmed polypropylene contains at least 50 mol% propylene and has a molecular weight distribution (Mw/Mn) ranging from 7 to 22, a z-average molecular weight of less than 2,500,000g/mol, a branching index (g' vis ) And a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃. The base or trimmed polypropylene may be produced from one or more high melt strength polypropylenes (HMS PP).)

1. A polypropylene composition comprising:

a base polypropylene comprising at least 50 mol% propylene content and having:

a molecular weight distribution (Mw/Mn) of 7 to 22,

a z-average molecular weight of less than 2,500,000g/mol,

branching index (g ') greater than or equal to 0.95'_vis) And are and

a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃; and

a clarifying agent.

2. The polypropylene composition of claim 1, wherein the base polypropylene comprises a trimmed polypropylene (tPP).

3. The polypropylene composition of claim 1 or 2, wherein the tPP is produced from a high melt strength polypropylene (HMS PP).

4. The polypropylene composition according to any one of claims 1 to 3, comprising 50ppm to 5,000ppm of a clarifying agent.

5. The polypropylene composition of any one of claims 1 to 4, wherein the clarifying agent comprises sorbitol, benzoate, organophosphate, norbornyl diacid, esters thereof, salts thereof, or any combination thereof.

6. The polypropylene composition of any one of claims 1 to 5 wherein the clarifying agent comprises 1,2, 3-tridecyloxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol, an ester thereof or a salt thereof.

7. The polypropylene composition according to any one of claims 1 to 6, wherein the polypropylene composition has a haze value according to ASTM D1003 of less than or equal to 50%.

8. The polypropylene composition according to any one of claims 1 to 7, wherein the polypropylene composition has a haze value according to ASTM D1003 of from 1% to less than 30%.

9. The polypropylene composition according to any one of claims 1 to 8, wherein the polypropylene composition has a gloss value in the machine direction of more than 15 according to ASTM D2457.

10. The polypropylene composition according to any one of claims 1 to 9, wherein the polypropylene composition has a gloss value in the machine direction according to ASTM D2457 of from 20 to 70.

11. The polypropylene composition according to any one of claims 1 to 10, wherein the polypropylene composition has a gloss value in transverse direction according to ASTM D2457 of more than 15.

12. The polypropylene composition according to any one of claims 1 to 11, wherein the polypropylene composition has a gloss value in transverse direction according to ASTM D2457 of from 20 to 70.

13. The polypropylene composition according to any one of claims 1 to 12, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 20 ° of more than 10.

14. The polypropylene composition according to any one of claims 1 to 13, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 20 ° in the range of from 20 to 50.

15. The polypropylene composition according to any one of claims 1 to 14, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 60 ° of more than 20.

16. The polypropylene composition according to any one of claims 1 to 15, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 60 ° in the range of from 30 to 100.

17. The polypropylene composition according to any one of claims 1 to 16, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 85 ° of more than 75.

18. The polypropylene composition according to any one of claims 1 to 17, wherein the polypropylene composition has a gloss value according to ASTM D523 at an angle of 85 ° of from 80 to 100.

19. The polypropylene composition of any one of claims 1 to 18, wherein the polypropylene composition has a 1% secant flexural modulus in the machine direction or the transverse direction of greater than 200,000 psi.

20. The polypropylene composition of any one of claims 1 to 19, wherein the polypropylene composition has a 1% secant flexural modulus in the machine or transverse direction of from 215,000psi to 270,000 psi.

21. The polypropylene composition according to any one of claims 1 to 20, wherein the polypropylene composition is in the form of a blown film.

22. The polypropylene composition according to any one of claims 1 to 21, wherein the base polypropylene has a melt strength (190 ℃) in the range of 1cN to 15 cN.

23. The polypropylene composition according to any one of claims 1 to 22, wherein the crystallization temperature Tc of the base polypropylene is above 114 ℃.

24. The polypropylene composition of any one of claims 1 to 23, wherein the second peak melting temperature (Tm) of the base polypropylene₂) Greater than 157 ℃.

25. The polypropylene composition according to any one of claims 1 to 24, wherein the base polypropylene has an Mz/Mn value of less than 60.

26. The polypropylene composition according to any one of claims 1 to 25, wherein the Mz/Mw value of the base polypropylene is less than 4.

27. The polypropylene composition of any one of claims 1 to 26, wherein the base polypropylene has a tan δ of greater than 4.

28. A method of forming a film comprising extruding the polypropylene composition of any one of claims 1 to 27 through a die opening to form a film.

29. A method of forming a finished film, the method comprising:

extruding a molten polypropylene composition comprising a base polypropylene and a clarifying agent through a die opening to form a film, wherein the base polypropylene comprises at least 50 mol% propylene and has:

a molecular weight distribution (Mw/Mn) of 7 to 22,

a z-average molecular weight of less than 2,500,000g/mol,

a branching index (g ') of at least 0.95'_vis) And are and

a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃; and

the film is cooled at a distance away from the die opening to produce a finished film.

30. A method of forming a finished film, the method comprising:

trimming a high melt strength polypropylene (HMS PP) to produce a trimmed polypropylene (tPP);

extruding a molten polypropylene composition comprising tPP and a clarifying agent through a die opening to form a film, wherein the tPP comprises at least 50 mol% propylene and has:

a molecular weight distribution (Mw/Mn) of 7 to 22,

a z-average molecular weight of less than 2,500,000g/mol,

at least 0.95 branchConversion index (g'_vis) And are and

a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃; and

the film is cooled at a distance away from the die opening to produce a finished film.

31. The method of claim 29 or 30, wherein cooling the film comprises blowing air over at least a portion of the film.

Technical Field

The present disclosure provides polypropylene-based material-containing compositions and methods of forming films therefrom.

Background

In the production of polymeric films, particularly blown films, polymers with good processability are desired to achieve commercial production rates while maintaining sufficient melt strength, e.g., bubble stability. In addition, good physical properties (e.g., stiffness, roughness, or tear strength) of the final film product are desirable. Based on the balance of properties, certain high melt strength polypropylenes (HMS PP) appear to be good candidates for blown film applications. It was observed that the broad molecular weight distribution (Mw/Mn, or "MWD") of such HMS PP provides shear thinning, and the presence of a high molecular weight tail provides sufficient melt strength and high stiffness for such films.

However, it has been found that some polypropylenes having a high molecular weight tail during the film blowing process, despite having good melt strength and shear thinning, exhibit surface and bulk irregularities (e.g., wrinkled appearance or melt fracture) even when processed at low shear rates (below the commercial range of 13 lb/hr/in). In addition, films formed from these polypropylenes can have low gloss and high haze, and thus exhibit opacity.

Accordingly, there is a need for improved polypropylene compositions having desirable melt strength, high stiffness and gloss, and minimal or no haze, and methods of blowing films from the polypropylene compositions.

Summary of The Invention

The present disclosure provides a polypropylene composition comprising one or more base polypropylenes and one or more clarifying agents. The base polypropylene preferably contains at least 50 mol% propylene and has a molecular weight distribution (Mw/Mn) in the range of from 7 to 22, a z-average molecular weight of less than 2,500,000g/mol, a branching index (g'_vis) And a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃. The polypropylene composition maintains high stiffness, high temperature resistance, high gloss, and minimal or no haze.

In one or more embodiments, the method of forming a film comprises extruding a polypropylene composition through one or more die openings to form a film. For example, the method can include extruding a molten polypropylene composition comprising one or more base polypropylenes and one or more clarifiers through a die opening to form a film, and cooling the film at a distance away from the die opening to produce a finished film. The film may be cooled by blowing air, nitrogen, argon or other gas over at least a portion of the film.

In any embodiment, the method of forming a film comprises trimming a high melt strength polypropylene (HMS PP) to produce a trimmed polypropylene (tPP) and extruding the tPP to form the film. For example, the process comprises extruding a molten polypropylene composition comprising one or more tpps and one or more clarifiers through a die opening to form a film, and cooling the film at a distance away from the die opening to produce a finished film.

Brief Description of Drawings

So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

The figure is a bar graph depicting 1% secant flexural modulus, along with haze and gloss values, in the machine direction and cross direction for a propylene composition, according to one or more embodiments.

To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

Detailed Description

The present disclosure provides a polypropylene composition that can have high gloss and minimal or no haze, while also having high melt strength (e.g., high temperature resistance) and high stiffness. The polypropylene composition may contain one or more base polypropylenes and one or more clarifying agents, and may be in the form of a blow mold. In any of the embodiments, the embodiments so disclosed are polypropylene compositions (or consisting of, or consisting essentially of) a base polypropylene comprising at least 50 mol% propylene content and having a molecular weight distribution (Mw/Mn) of from 7 to 22, a z-average molecular weight of less than 2,500,000g/mol, a branching index (g'_vis) And a melt strength of less than 20cN determined using an extensional rheometer at 190 ℃.

The polypropylene composition may have a haze value of less than or equal to 50%, for example from 0.5%, 1%, 2%, 3%, 5%, 8%, 10%, or 12% to 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% according to ASTM D1003. In some examples, the polypropylene composition can have a haze value of less than 10%, less than 12%, less than 15%, less than 18%, less than 20%, less than 25%, less than 30%, less than 35%, less than 40%, less than 45%, or less than 50% according to ASTM D1003. For example, the polypropylene composition may have a haze value according to ASTM D1003 of 0.5% to 50%, 1% to less than 50%, 5% to less than 50%, 10% to less than 50%, 15% to less than 50%, 20% to less than 50%, 30% to less than 50%, 1% to less than 30%, 5% to less than 30%, 10% to less than 30%, 15% to less than 30%, 20% to less than 30%.

The polypropylene composition may have a gloss value in the machine direction of greater than 15, for example 18, 20, 25, 30, or 35 to 40, 45, 50, 55, 60, 65, or 70 according to ASTM D2457. For example, the polypropylene composition may have a gloss value in the machine direction of 18 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 18 to 60, 20 to 60, 30 to 60, 40 to 60, or 50 to 60 according to ASTM D2457.

The polypropylene composition may have a gloss value in the cross direction of greater than 15, for example 18, 20, 25, 30, or 35 to 40, 45, 50, 55, 60, 65, or 70 according to ASTM D2457. For example, the polypropylene composition may have a gloss value in the cross direction of 18 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 18 to 60, 20 to 60, 30 to 60, 40 to 60, or 50 to 60 according to ASTM D2457.

The polypropylene composition may have a gloss value of greater than 10, for example 12, 15, 18, 20, or 25 to 30, 35, 40, 45, or 50 at an angle of 20 ° according to ASTM D523. For example, the polypropylene composition may have a gloss value of greater than 10 to 50, greater than 10 to 40, greater than 10 to 30, greater than 10 to 20, 20 to 50, 20 to 40, or 20 to 30 at an angle of 20 ° according to ASTM D523.

The polypropylene composition may have a gloss value according to ASTM D523 of greater than 20, for example 25, 30, 35, 40, 45, or 50 to 60, 70, 80, 90, or 100 at an angle of 60 °. For example, the polypropylene composition may have a gloss value at an angle of 60 ° of greater than 20 to 100, greater than 20 to 90, greater than 20 to 80, greater than 20 to 70, greater than 20 to 60, greater than 20 to 50, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, or 30 to 50 according to ASTM D523.

The polypropylene composition may have a gloss value according to ASTM D523 of greater than 70 or greater than 75, for example 60, 65, 70, or 75 to 80, 85, 90, 95, or 100 at an angle of 85 °. For example, the polypropylene composition may have a gloss value at an angle of 85 ° of greater than 70 to 100, greater than 75 to 100, greater than 80 to 100, greater than 85 to 100, greater than 90 to 100, 75 to 100, 80 to 100, 85 to 100, or 90 to 100 according to ASTM D523.

The polypropylene composition can have a 1% secant flexural modulus in each of the machine direction or the cross direction (or independently) of greater than 200,000psi, e.g., 210,000psi, 215,000psi, 220,000psi, 225,000psi, 230,000psi, or 240,000psi to 245,000psi, 250,000psi, 260,000psi, 270,000psi, 275,000psi, 280,000psi, 290,000psi, or 300,000 psi. For example, the polypropylene composition can have a 1% secant flexural modulus in each of the machine direction or the cross direction (or independently) of greater than 200,000psi to 300,000psi, 210,000psi to 290,000psi, 215,000psi to 290,000psi, 225,000psi to 290,000psi, 240,000psi to 290,000psi, 250,000psi to 290,000psi, 260,000psi to 290,000psi, 280,000psi to 290,000psi, 215,000psi to 275,000psi, 225,000psi to 275,000psi, 240,000psi to 275,000psi, 250,000psi to 275,000psi, or 260,000psi to 275,000 psi. The 1% secant flexural modulus was determined by the ExxonMobil secant/tensile standard as provided in the experimental section below.

The polypropylene composition can have a yield strength in each of the machine direction or the cross direction (or independently) of greater than 4,000psi, 4,500psi, 5,000psi, 5,500psi, or 6,000 psi. In one or more examples, the yield strength of the polypropylene composition in each of the machine direction or the cross direction (or independently) can be 4,000psi, 4,500psi, 5,000psi, 5,200psi, 5,400psi, or 5,500psi to 5,600psi, 5,800psi, 6,000psi, 6,100psi, 6,200psi, 6,300psi, or 6,500 psi. For example, the polypropylene composition has a yield strength in each of the machine direction or the cross direction (or independently) of 4,000psi to 6,500psi, 4,500psi to 6,500psi, 5,000psi to 6,500psi, 5,200psi to 6,500psi, 5,400psi to 6,500psi, 5,500psi to 6,500psi, 5,600psi to 6,500psi, 5,800psi to 6,500psi, 4,000psi to 6,300psi, 4,500psi to 6,300psi, 5,000psi to 6,300psi, 5,200psi to 6,300psi, 5,400psi to 6,300psi, 5,500psi to 6,300psi, 5,300 psi to 6,300psi, 5,600psi to 6,300psi, or 5,800 to 6,300 psi.

The polypropylene composition may have an elongation at yield in each of the machine direction or the cross direction (or independently) of greater than 5, 5.1, or 5.2 to 5.4, 5.5, 5.6, or 5.7. In one or more examples, the polypropylene composition has an elongation at yield in each of the machine direction or the cross direction (or independently) of 5 to 6,5 to 5.8, 5 to 5.7, 5 to 5.6, 5 to 5.5, 5.2 to 6, 5.2 to 5.8, 5.2 to 5.7, 5.2 to 5.6, or 5.2 to 5.5.

The polypropylene composition may have a tensile strength in each of the machine direction or the cross direction (or independently) of greater than 5,000psi, 5,500psi, 5,800psi, 6,000psi, 6,200psi, 6,400psi, or 6,500 psi. In one or more examples, the polypropylene composition has a tensile strength in each of the machine direction or the cross direction (or independently) of 5,000psi, 5,200psi, 5,400psi, 5,500psi, or 5,600psi to 5,800psi, 6,000psi, 6,100psi, 6,200psi, 6,300psi, 6,400psi, 6,500psi, 6,600psi, or 6,700 psi. For example, the polypropylene composition has a tensile strength in each of the machine direction or the cross direction (or independently) of 5,000psi to 6,700psi, 5,000psi to 6,600psi, 5,200psi to 6,600psi, 5,400psi to 6,600psi, 5,500psi to 6,600psi, 5,600psi to 6,600psi, 5,800psi to 6,600psi, 5,200psi to 6,400psi, 5,400psi to 6,400psi, 5,500psi to 6,400psi, 5,600psi to 6,400psi, or 5,800psi to 6,400 psi.

The polypropylene composition may have an elongation at break in the machine direction of greater than 400, 420, or 430 to 435, 440, 450, 460, 470, 480, 490, or 500. In one or more examples, the polypropylene composition has an elongation at break in the machine direction of 400 to 500, 420 to 490, 430 to 490, 440 to 450, 460 to 490, 420 to 480, 430 to 480, 440 to 480, or 460 to 480.

The polypropylene composition may have an elongation at break in the cross direction of more than 5 or 6 to 7,8, or 9. In one or more examples, the polypropylene composition has an elongation at break in the cross direction of 5 to 9, 5 to 8, 5 to 7, 6 to 9, 6 to 8, 6 to 7,7 to 9, or 7 to 8.

Base polypropylene

The compositions of the present disclosure include one or more base polypropylenes. The "base polypropylene" may be or include one or more trimmed polypropylenes (tpps). tPP contains and/or is produced from one or more high melt strength polypropylenes (HMSPP), as described and discussed herein.

The terms "trim," "trimmed," and "trimmed" as used herein refer to the reduction of the high molecular weight tail of a polymer, either chemically or by dilution, as evidenced by a reduction in the z-average molecular weight of the polymer, independently and with respect to the number average and weight average molecular weights. In one or more instances, the terms "trim," "trimmed," and "trimmed" may refer to chemical reduction.

As used herein, a "film" or "multilayer film" is a material having an average thickness of less than or equal to 0.25mm and may include one or more substances, such as polymers, fillers, oils, antioxidants, antistatic agents, antiblocking agents, or any combination thereof, and may be continuous, typically flexible, in its measurable width and length, such as a thickness ranging from 2 μm, 10 μm, 20 μm, or 40 μm to 50 μm, 100 μm, 150 μm, 200 μm, or 250 μm. The term "film" also includes the possibility of coating, for example when the film is extruded onto a surface such as metal, glass, another polymer, or other rigid or flexible surface.

The pruning of HMS PP can be performed by chemical treatment with long half-life organic peroxides, by physical dilution with narrow Molecular Weight Distribution (MWD) polypropylene, or a combination of both. In one or more embodiments, the HMS PP described herein is trimmed only by treatment with long half-life organic peroxides. In one or more embodiments, the process for making tPP includes combining a propylene containing at least 50 mol% and having a molecular weight distribution (Mw/Mn) greater than 6, a branching index (g'_vis) And measured using an extensional rheometer at 190 ℃ toHMS PP high melt strength polypropylene (HMS PP) with a melt strength of less than 20cN with (i) a long half-life organic peroxide in the range of 20 to 1000 ppm; and/or (ii) in the range of from 20 to 70 wt% of a narrow MWD polypropylene comprising at least 50 mol% propylene and having a molecular weight distribution (Mw/Mn) of less than 6; and isolating the trimmed polypropylene. Other properties of the starting HMS PP as well as tPP will be described below.

In one or more embodiments, the tPP contains at least 50 mol% propylene and has a molecular weight distribution (Mw/Mn) of less than 22, 20, 18, 16, or 15, or ranging from 5,6, 7, 7.5, 8, 8.5, or 9 to 15, 16, 18, 20, or 22, a z-average molecular weight of less than 2,500,000g/mol, 2,000,000g/mol, 1,600,000g/mol, 1,400,000g/mol, or 1,200,000g/mol, or ranging from 500,000g/mol, 600,000g/mol, or 800,000g/mol to 1,200,000g/mol, 1,400,000g/mol, or 1,600,000 g/mol; a branching index (g ') of at least 0.95'_vis) And a melt strength of at least 20cN (e.g., in the range of 1cN to 15cN) determined using an extensional rheometer at 190 ℃. Other properties of tPP will be described below.

By diluting the concentration of high molecular weight chains in a polymer, such as HMS PP with a high molecular weight component or "tail", for example by blending HMS PP with narrow MWD homopolymer PP, it has been found that the quality of the film is improved and that there are no surface/bulk irregularities at commercial film formation rates of at least 13 lb/hr/in. It has been found that peroxides having a relatively "long" half-life can be made available by the addition of low levels of peroxides (e.g., Luperox)^TM 101，Triganox^TM101) The concentration of the high molecular weight tail is reduced. Using this method, the film quality of the HMS PP containing film is improved without surface/bulk irregularities at commercial film formation rates of at least 13 lb/hr/in.

High melt strength polypropylene (HMS PP)

tPP and films (or coatings) derived therefrom are derived from polypropylene having a relatively high melt strength (greater than 15, or 20cN), herein referred to simply as "high melt strength polypropylene" (or HMS PP), which has certain desirable characteristics as described herein and is prepared in accordance with the disclosure in WO 2014/070386. In one or more embodimentsIn one embodiment, the HMS PP comprises at least 50 mol%, 60 mol%, 70 mol%, 80 mol%, or 90 mol% propylene-derived monomer units, or units ranging from 50 mol%, 60 mol%, or 80 mol% to 95 mol%, 97 mol%, or 99 mol% propylene-derived units, with the remainder of the monomer units selected from ethylene and C₄-C₂₀Alpha-olefins, such as ethylene or 1-butene. In one or more embodiments, the HMS PP is a homopolymer of propylene-derived monomer units.

In one or more embodiments, by¹³The isotactic pentad percentage of HMS PP determined by C NMR spectroscopy is greater than 90%, 92%, or 95%. Further, the Melt Flow Rate (MFR) of the HMS PP ranges from 0.1, 1, or 2g/10min to 12, 16, 20, or 40g/10min, as determined according to ASTM D1238 condition L (230 ℃/2.16 kg).

In one or more embodiments, the HMS PP has a weight average molecular weight (Mw) ranging from 200,000g/mol, 300,000g/mol, or 350,000g/mol to 500,000g/mol, 600,000g/mol, or 700,000 g/mol; a number average molecular weight range (Mn) from 15,000g/mol or 20,000g/mol to 30,000g/mol, 35,000g/mol, or 40,000 g/mol; and/or the z-average molecular weight ranges from 900,000g/mol, 1,000,000g/mol, or 1,200,000g/mol to 1,800,000g/mol, 2,000,000g/mol, or 2,200,000g/mol, as determined by size exclusion chromatography ("SEC"). In one or more embodiments, the HMS PP has a molecular weight distribution (Mw/Mn) of greater than 6,7, or 8; or ranges from 6,7, 8, 10, or 12 to 14, 16, 18, 20, or 24. In one or more embodiments, the Mz/Mw of the HMS PP is greater than 3, 3.4, or 3.6, or ranges from 3, 3.4, or 3.6 to 3.8, 4, or 4.4. The Mz/Mn of the HMS PP may be greater than 35, 40, 55, or 60, or range from 35, 40, or 55 to 60, 65, 70, 75, or 80. The molecular weight (weight average molecular weight Mw, number average molecular weight Mn, and z-average molecular weight Mz) and the molecular weight distribution (Mw/Mn) of the polymer were determined using SEC. The apparatus includes a high temperature size exclusion chromatograph (from either Waters Corporation or Polymer Laboratories) with a differential refractive index Detector (DRI) or Infrared (IR) detector.

HMS PP can be linear, as evidenced by a high branching index.In one or more embodiments, the branching index (g ', also referred to in the literature as g ') of the HMS PP '_{vis avg}) Is at least 0.95, 0.97, or 0.98 as determined in US 7,807,769 column 37 by using a high temperature size exclusion chromatograph (from Waters Corporation or Polymer Laboratories) equipped with three online detectors, a differential refractive index Detector (DRI), a Light Scattering (LS) detector, and a viscometer.

In one or more embodiments, the melt strength of the HMS PP may be at least 15cN or 20 cN; or ranging from 10cN, 15cN, or 20cN to 35cN, 40cN, 60cN, 80cN, or 100cN, as determined using an extensional rheometer at 190 ℃.

In one or more embodiments, the HMS PP has a viscosity ratio ranging from 35 to 80 as determined by the complex viscosity ratio at a fixed strain of 10% at an angular frequency of 0.01 to 100rad/s at 190 ℃. Further, in one or more embodiments, the HMS PP has a peak extensional viscosity (annealed) at a strain rate (190 ℃) of 0.01/sec ranging from 10 or 20 to 40, 50, 55, 60, 80, or 100kPa · s.

In one or more embodiments, the HMS PP has a heat distortion temperature of greater than or equal to 100 ℃ as determined according to ASTM D648 using a load of 0.45MPa (66 psi). In any embodiment, the HMS PP has a modulus ranging from 1800 or 2000MPa to 2400 or 2500MPa, as determined according to ASTM D790A on nucleated samples containing 0.01 to 0.1 wt% of an alpha-nucleating agent.

Peak melting point temperature (second melt, Tm) of HMS PP₂) May be greater than 160, or 164 ℃, or range from 160, or 164 ℃ to 168, or 170 ℃ (by DSC); and a crystallization temperature (Tc) greater than 100 ℃, 105 ℃, or 110 ℃, or ranging from 100 ℃, or 105 ℃, or 110 ℃ to 115 ℃, or 120 ℃ (by DSC).

In one or more embodiments, the HMS PP used to make tPP and the films derived therefrom is a reactor grade material, which means that the HMS PP is used as it comes out of the reactor used to produce it, which is optionally further made into pellets of material that have not been altered in any of its properties, such as branching index, MWD, or melt flow rate, by more than 1% of its starting value. In one or more embodiments, the HMS PP is not crosslinked or reacted with any radiation or chemical to cause crosslinking and/or long chain branching. Typical forms of radiation known to cause cross-linking and/or long chain branching include the use of so-called electron beams or other radiation (beta or gamma rays) that interact with the polymer.

Process for producing trimmed polypropylene

As described above, the process of making tPP can include combining HMS PP with either a long half-life organic peroxide, a narrow MWD polypropylene, or a combination thereof. Combining the long half-life organic peroxide with the HMS PP such that it ranges from 20ppm, 25ppm, or 50ppm to 400ppm, 600ppm, 800ppm, or 1,000ppm of the long half-life organic peroxide, based on the weight of the peroxide, HMS PP, and any other additives. "Long half-life organic peroxide" is an organic peroxide (peroxide-containing hydrocarbon) having a1 hour half-life temperature¹t_1/2) Greater than 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, as measured in a C6-C16 alkane, such as dodecane or decane, or a halogenated aryl compound, such as chlorobenzene.

Such peroxides may include compounds having the general structure R¹-OO-R²Or R is¹-OO-R³-OO-R²Or more generally (R)¹-OO-R²)_nWherein "n" is an integer from 1 to 5; and wherein R¹And R²Each independently selected from C2 to C10 alkyl, C6 to C12 aryl, and C7 to C16 alkylaryl, e.g., iso-or tertiary alkyl, and R³Selected from C1 to C6, or C10 alkylene, C6 to C12 aryl, and C7 to C16 alkylaryl; "-OO-" is a peroxide moiety. The long half-life organic peroxide may be 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, di-t-butylperoxide, or dicumyl peroxide.

The half-life is determined by differential scanning calorimetry-thermal activity monitoring of a dilute solution of the initiator in a suitable solvent. The half-life can then be calculated from an arrhenius plot as is well known in the art. Thus, by treating HMS PP with a large amount of high molecular weight component or "tail" with a long half-life peroxide, the high molecular weight component is reduced or "trimmed". Suitable solvents are determined based on the solubility of the organic peroxide.

Alternatively or additionally, the HMS PP may be trimmed by incorporating a "narrow MWD polypropylene" in the range of from 20 wt% or 30 wt% to 50 wt%, 60 wt%, or 70 wt%, based on the weight of the combined components. Narrow MWD polypropylene contains at least 50 mol%, 60 mol%, 70 mol%, 75 mol%, or 80 mol% propylene and has a MWD less than 6, or 5, or 4, or ranges from 2, or 2.5 to 4, or 5, or 6. In one or more embodiments, the MFR of the narrow MWD polypropylene ranges from 4g/10min or 8g/10min to 40g/10min, 60g/10min, 80g/10min, or 100g/10 min. The narrow MWD polypropylene may be a propylene polymer having at least 50 mol% propylene derived units, such as those containing from 0.1 to 5 wt% of comonomer, e.g. ethylene derived units, e.g. a propylene homopolymer, e.g. isotactic polypropylene. Thus, the high molecular weight component of HMS PP can be diluted or "trimmed" using such techniques. "trimming" includes combining the HMS PP with the narrow MWD polypropylene by melt blending as known in the art, e.g. one or two pass through an extruder, e.g. the "two pass" process described in WO2016053468a 1.

In one or more embodiments, "bonding" of the HMS PP to the long half-life organic peroxide may be performed by melt blending at least the peroxide and the HMS PP at a melting temperature of the HMS PP, e.g., at a temperature of at least 120 ℃, 130 ℃, 150 ℃, or 160 ℃, e.g., at a temperature ranging from 120 ℃, 130 ℃, 140 ℃, 150 ℃, or 160 ℃ to 220 ℃, 240 ℃, 260 ℃, 280 ℃, or 300 ℃, wherein such temperature is the melt temperature measured by a thermocouple in the melt when extruded in a mixing device used to bond the materials. In some examples, the melt temperature of any melt comprising HMS PP ranges from 245 ℃, or 250 ℃ to 260 ℃. At such temperatures the long half-life organic peroxide is activated by beta-shear towards the polypropylene and at the low concentrations used to achieve pruning, where the amount and binding temperature are adjusted to the pruning level for the particular HMS PP. The incorporation can be carried out in a single or twin screw extruder which can have controlled heating capabilities. This process can be carried out to form tPP pellets, or to fit film making equipment or other desired end use product production equipment such as thermoforming or blow molding.

Trimmed polypropylene (tPP)

The method of combining long half-life organic peroxide with HMS PP yields tPP. The starting polypropylene used to prepare tPP typically has a significant amount of high molecular weight polymer chains, typically above the critical orientation level. When certain articles, such as films, are manufactured, this can result in strong films, but have many surface defects and are therefore unusable for most applications. It has been found that if some of the high molecular weight components are reduced or removed, trimmed, the resulting tPP may have certain desirable properties, but still retain other desirable properties.

In one or more embodiments, tPP has a melt strength (measured as described herein at 190 ℃) of less than 20cN, 15cN, or 10cN, or ranging from 1cN or 2cN to 4cN, 6cN, 10cN, 15cN, or 20 cN. the crystallization temperature Tc (as measured by DSC) of tPP is greater than 114 ℃, 115 ℃, or 116 ℃; or ranges from 114 ℃, 115 ℃, or 116 ℃ to 120 ℃, 122 ℃, or 124 ℃. Second peak melting temperature Tm of tPP₂(as measured by DSC) greater than 157 ℃, or 158 ℃, or 159 ℃, or ranges from 157 ℃, 158 ℃, or 159 ℃ to 166 ℃, 167 ℃, 168 ℃, or 169 ℃.

In one or more embodiments, the branching index (g ', also referred to in the literature as g ') of tPP '_{vis avg}) Is at least 0.95, 0.97, or 0.98. tpps have molecular weight characteristics that are distinct from the HMS PPs from which they are derived. In one or more embodiments, the z-average molecular weight of the tPP is less than 2,500,000g/mol, 2,000,000g/mol, 1,600,000g/mol, 1,400,000g/mol, or 1,200,000g/mol, or ranges from 500,000g/mol, 600,000g/mol, or 800,000g/mol to 1,200,000g/mol, 1,400,000g/mol, 1,600,000g/mol, 2,000,000g/mol, or 2,500,000 g/mol. the Mz/Mn value of tPP is less than 60, 55, or 40, or ranges from 10, 15, 20, or 25 to 354055, or 60. the Mz/Mw value of tPP is less than 4, 3.8, or 3.6, or ranges from 2.5 or 2.6 to 3.6, 3.8, or 4. the molecular weight distribution (Mw/Mn) of tPP is less than 22, 20, 18, 16, or 15, or ranges from 5,6, 7, 7.5, 8, 8.5, or 9 to 15, 16, 18, 20, or 22.

In one or more embodiments, the MFR (2.16kg/230 ℃) of the tPP ranges from 0.2g/10min, 0.5g/10min, 1g/10min, 2g/10min, or 3g/10min to 4g/10min, 5g/10min, 6g/10min, 8g/10min, 10g/10min, or 20g/10 min. For example, the MFR of tPP is from 0.2g/10min to 20g/10min, from 0.5g/10min to 15g/10min, from 0.5g/10min to 10g/10min, from 0.5g/10min to 8g/10min, from 0.5g/10min to 5g/10min, from 0.5g/10min to 4g/10min, from 0.5g/10min to 3g/10min, or from 0.5g/10min to 2g/10 min. tPP can be elastomeric while in the melt phase. In one or more embodiments, the trimmed polypropylene has a Tan δ (ratio of viscous modulus (G ") to elastic modulus (G'), which is a useful measure of the presence and degree of elasticity in the melt) of greater than 4,6, 8, or 10, or ranging from 4,6, 8, or 10 to 20, 24, 28, 32, or 36.

tPP also has favorable bulk-physical properties. In one or more embodiments, the modulus of tPP is greater than 13MPa, 14MPa, or 15MPa, or ranges from 13MPa, 14MPa, or 15MPa to 18MPa, 20MPa, 22MPa, or 24 MPa. In one or more embodiments, like the base HMS PP, the reaction product of a multifunctional monomer (e.g., multifunctional acrylate) or oligomer (e.g., polyisobutylene), or a crosslinker (e.g., silane, siloxane) is not present in tPP.

Clarifying and nucleating agents and other additives

It has been found that by including a comonomer in the polypropylene and/or a clarifying agent in the polypropylene composition, the stiffness and high temperature resistance of the base polypropylene (and polypropylene composition) can be maintained while improving clarity (e.g., high gloss and minimal or no haze). Without being bound by theory, it is believed that the inclusion of a comonomer within the polypropylene and/or the inclusion of a clarifying agent within the polypropylene composition introduces defects into the crystal structure of the base polypropylene. This provides a reduction of up to 10% or 20% or more in the thickness dimension of the base polypropylene and/or the thickness of the material from which the desired article is made. Therefore, the food container and the packaging material can be made lighter without losing their stiffness and durability. The polypropylene compositions described herein are particularly useful for any shaped article where clarity is desired, particularly thermoformed articles, sheets, and films, as well as articles comprising sheets and films of materials. Examples of articles of manufacture include food containers, bottles, compact disc containers (compact disc containers), medical containers and devices, housings for electronic devices, and other consumer and commercial items.

The term "clarifying agent" or "clarifying agent" as used herein refers to a chemical agent that improves (reduces) the haze of a polyolefin sample (e.g., base polypropylene), as tested in accordance with ASTM D1003. For example, the agent may be an agent that increases the rate of crystallization of the polyolefin relative to the polyolefin without the agent. The clarifying agent can be a compound having a chemical formula such as k.hoffman, g.ribbon and D.One or more compounds of the properties described in 176 machine ol. symp.83-91 (2001). Exemplary clarifying agents can be or include one or more benzoates (e.g., sodium and/or potassium benzoate), stearates (e.g., zinc stearate), sorbitol, organophosphates, norbornanedioic acid, metal tert-butylbenzoates, esters thereof, salts thereof, or any combination thereof. In one or more examples, the fining agent can be or include 1,2, 3-tridecyloxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene]-nonanol (TBPMN), an ester thereof, or a salt thereof. For example, the clarifying agent may be or compriseNX^TM8000 clarifying agent and/orHPN-600ei nucleating agents, both commercially available from Milliken&Company, and/orXT-386 clarifying agent, commercially available from BASF, SE. In some examples, the molecular weight of the clarifying agent used herein is less than 1,000g/mol, 800g/mol, or 500g/mol, and is, for example, at least 50g/mol, 80g/mol, or 100 g/mol. Clarifying agents can also increase the stiffness of polypropylene.

In one or more embodiments, the polypropylene composition contains one or more clarifying agents in an amount ranging from 50ppm, 100ppm, 150ppm, 200ppm, 300ppm, 350ppm, 400ppm, 420ppm, 450ppm, 500ppm, 750ppm, or 1,000ppm to 1,500ppm, 2,000ppm, 2,500ppm, 3,000ppm, 4,000ppm, 4,500ppm, or 5,000 ppm. For example, the polypropylene composition contains 50ppm to 5,000ppm, 100ppm to 5,000ppm, 150ppm to 5,000ppm, 200ppm to 5,000ppm, 300ppm to 5,000ppm, 420ppm to 5,000ppm, 500ppm to 5,000ppm, 1,000ppm to 5,000ppm, 1,500ppm to 5,000ppm, 2,000ppm to 5,000ppm, 2,500ppm to 5,000ppm, 3,000ppm to 5,000ppm, 50ppm to 3,000ppm, 100ppm to 3,000ppm, 150ppm to 3,000ppm, 200ppm to 3,000ppm, 300ppm to 3,000ppm, 420ppm to 3,000ppm, 500ppm to 3,000ppm, 1,000ppm to 3,000ppm, 1,500ppm to 3,000ppm, 2,000ppm to 3,000ppm, or 2,500ppm to 3,000ppm of a clarifying agent.

In any embodiment, other "additives" may also be present in the polypropylene composition and/or film thereof. For example, the polypropylene composition may comprise up to 1 wt%, 2 wt%, or 3 wt% of additives. These additives may be added before, during or after forming the coextruded sheet or film. Such additives include antioxidants (e.g., hindered phenol-type and phosphite-type compounds), stabilizers such as lactones and vitamin E, nucleating agents (both alpha-nucleating agents and beta-nucleating agents), colorants (dyes or pigments), fillers (silica or talc), UV stabilizers, mold release agents, adhesion promoters, antistatic agents, acid scavengers (e.g., calcium stearate), antiblocking agents, antihalation agents, or combinations thereof.

In one or more embodiments, no nucleating agent is present, e.g., no alpha-nucleating agent is present, meaning that no nucleating agent is added to the composition or any component of the composition at any stage of the formation process. Examples of alpha-nucleating agents include salts of monocarboxylic and polycarboxylic acids, sorbitol, such as dibenzylidene sorbitol, salts of phosphodiesters, vinyl cycloalkane polymers, or combinations thereof.

The polypropylene compositions of the present disclosure are particularly useful in films and articles comprising films or film coatings. Films having an average thickness of less than 250 μm can be made using the polypropylene composition and can contain any number of layers, such as additional layers of LLDPE, HDPE, LDPE, iPP, EP copolymers, and combinations thereof. Further, the transparent polypropylene can contain a composition comprising any of these polymers or combinations of polymers, and can be present in any desired amount. Further, the polypropylene compositions described herein can be used to make sheets having an average thickness of greater than or equal to 250 μm, or the sheets can contain one or more layers comprising the polypropylene composition and another material such as LLDPE, HDPE, LDPE, iPP, EP copolymers, and combinations thereof. Such sheets or other desired structures made using the polypropylene compositions described herein can be thermoformed, blow molded, or injection molded into useful articles, and further, the polypropylene compositions can be rotomolded to form useful articles.

The various descriptive elements and numerical ranges disclosed herein for the polypropylene composition and the method of forming the polypropylene composition and the films resulting therefrom may be combined with other descriptive elements and numerical ranges to describe the present invention; further, any upper value, including those described in the examples, can be combined with any lower value, given the element under consideration, in jurisdictions where such combinations are permitted. Features of the invention are shown in the following non-limiting examples.

Film formed from polypropylene composition

Many articles such as thermoformed articles, blow molded articles, injection molded articles, sheets, fibers, fabrics, and other useful articles can be formed from the polypropylene compositions described herein. The polypropylene composition may be formed into a film, particularly a cast film, an extrusion coated film, and a blown film, and/or included as at least a portion of one or more layers of a multilayer film, using any suitable method. Such films may have, for example, two, three, four or more layers represented by S/C, S/C, S/T/C/S, S/T/C/T/S, where "C" is the core layer, "T" is the tie layer, and "S" is the skin layer, each of which may be made of the same or different materials. Any one or more of the layers may comprise, consist essentially of, or consist of one or more polypropylene compositions. In some examples, structures include those containing a layer ranging from 50 wt%, 55 wt%, or 60 wt% to 80 wt%, 85 wt%, or 90 wt% of one or more polypropylene compositions, based on the weight of the components in the layer. In other examples, the layer is a core layer and the at least one skin layer comprises polyethylene and/or polypropylene. The polypropylene composition can replace HDPE in many known film structures and allows for a 10% to 30% reduction in dimensional thickness relative to when HDPE is used.

The polypropylene composition may be used in the manufacture of blown films. The ingredients used to form the film in a typical blow mold process are added in any desired form, such as granules, into a hopper that feeds the materials into an extruder where the materials are melt blended by shear and/or heat at the desired temperature. The molten material is then fed, with or without filtration, to a die that may have only one cavity, or a die that has multiple cavities corresponding to each of the multiple layers that will form the film. The die is also heated to the desired temperature and then forced away from the die. The cooling of the formed film is carried out by means of an apparatus which blows air or one or more other gases (e.g. nitrogen, argon, mixtures thereof) which is at least 5 or 10 ℃ cooler than the ambient air, where "ambient air" is air which is at least 1 meter but less than 5 meters from the cooling apparatus. For example, air may be blown against the outside of the film, e.g., around the entire circumference formed by the film. Inside also air is blown through, which cools and blows the film up like a bubble/balloon. The film begins to expand and eventually cools and crystallizes to form a blown film. Conventional polypropylenes can be difficult to use in blow molding processes because they typically have a low melt strength, which will promote bubble, balloon or film rupture. However, the HMS PP of the present disclosure may provide improved melt strength for improved polypropylene-based blow molding processes. In addition, high melt strength polymers typically promote an increase in haze. However, the polypropylene compositions of the present disclosure may provide low haze in addition to high melt strength.

The performance of the film-formed polypropylene-containing composition can be characterized by its maximum die rate. The "maximum die rate" is the normalized extrusion rate by die size commonly used in the blown film industry. The maximum die rate used herein is expressed as follows: the maximum die speed [ lb/in-hr ] ═ the extrusion rate [ lb/hr ]/die circumference [ inch ]. Another definition of maximum die rate is expressed as follows: maximum die rate [ kg/mm-hr ] ═ extrusion rate [ kg/hr ]/die diameter [ mm ]. The maximum die rate at which the film is formed is greater than 13lb/in-hr (0.73kg/mm-hr), or 16lb/in-hr (0.90kg/mm-hr), or 24lb/in-hr (1.34kg/mm-hr), or ranges from 13lb/in-hr (0.73kg/mm-hr), or 16lb/in-hr (0.90kg/mm-hr), or 24lb/in-hr (1.34kg/mm-hr) to 30(1.69kg/mm-hr), or within 40lb/in-hr (2.25 kg/mm-hr). Note that for "maximum die rate" in english units, the die size is the die circumference, while in metric units the die size is the die diameter. Thus, for a die factor in lb/in-hr, the complete expression is lb/die circumference (in inches)/hr; whereas for a die factor in kg/mm-hr, the complete expression is kg/die diameter (in mm)/hr.

The polypropylene composition can be processed at advantageously low temperatures. In one or more embodiments, the transparent polypropylene can be processed, e.g., melt extruded, at a barrel temperature of less than 210 ℃,200 ℃, or 190 ℃, or ranging from 160 ℃ or 170 ℃ to 190 ℃,200 ℃, or 210 ℃, and at a die temperature of less than 210 ℃, or ranging from 190 ℃,200 ℃, or 205 ℃ to 210 ℃.

In one or more embodiments, a method of forming a finished film includes extruding molten transparent polypropylene through a die opening to form a film, and causing the film to advance in a direction away from the die opening, e.g., in a molten state, with partial melting or softening due to some partial cooling. The method further includes cooling the molten transparent polypropylene into a film form at a distance from the die opening, wherein the distance is adjusted to affect the properties of the film (e.g., allowing the molten transparent polypropylene to relax prior to hardening and/or crystallizing upon cooling) and separating the finished film therefrom.

In some examples, the method of forming a film comprises extruding transparent polypropylene through one or more die openings to form a film. For example, the method can include extruding molten transparent polypropylene comprising one or more base polypropylenes and one or more clarifiers through a die opening to form a film, and then cooling the film at a distance away from the die opening to produce a finished film. The film may be cooled by blowing air, nitrogen, argon or other gas over at least a portion of the film.

"extrusion" refers to forming a polymer and/or polymer blend into a melt, e.g., by heat and/or shear forces, and forcing it to blend with other polymers and/or components (e.g., polyethylene and modifiers), and then forcing it out of a die in a desired form or shape to affect the form or shape of the exiting polymer melt, e.g., into a film, e.g., a tubular film. Any suitable device, such as a single or twin screw extruder, or other melt blending device known in the art and which may be equipped with a suitable die, will suitably provide "extrusion".

By "at a distance from the die" is meant a "cooling device," e.g., a cooling ring that blows air over the formed film, is at least 1cm, 2cm, 4cm, or 8cm (or other distances described herein) from the die, e.g., as measured from the top or outer edge of the die to the base of the cooling device.

By "causing film advancement" is meant that the film formed from the hardened polyethylene from the die opening is drawn or pushed away from the die by mechanical action or by some other means, such as by air pressure (negative or positive) to produce a continuous finished film.

In a typical process, a polyethylene melt is extruded generally vertically through a die, such as an annular slot die, to form a thin walled tube. Cooling can be performed in air or other gas introduced into the center of the die by means of a ring to inflate the tube like a balloon. Cooling may also be provided by other means and the air may be nitrogen/oxygen or other gas or mixture of gases or liquids. Mounted on top of the die, a ring of high velocity air is blown over the hot film to cool the film. Cooling occurs at a distance of at least 1cm from the die as described above. The tube of film may then continue to cool upward until it can pass through the nip where it flattens, creating a "lay-flat" tube called a film. This collapsed or collapsed pipe can then be withdrawn from the extrusion "tower" by means of more rollers. On higher output production lines, the air within the bubbles is also exchanged. This is called IBC (internal bubble cooling).

The lay flat film is then either left as is or the lay flat edges are cut to produce two flat sheets of film and wound on a reel. Articles such as bags can be made from such flat-folded films. In this regard, if held in a flat fold, the tube of film is made into bags by sealing and cutting or perforating across the width of the film to make each bag. This is either done together with the blown film process or at a later stage.

In some examples, the expansion ratio between the die and the blown tube of the film will be 1.5 to 4 times the diameter of the die. The film is blown at a temperature of from 400 ° F (204 ℃) to 500 ° F (260 ℃), for example from 410 ° F (210 ℃) to 465 ° F (241 ℃). The draw between the melt wall thickness and the cooling film thickness occurs in both the radial and longitudinal directions and is easily controlled by varying the volume of air inside the bubble and by varying the extraction speed. This gives a blow mould a better balance of properties than a conventional cast or extruded film which is drawn only in the direction of extrusion.

Examples

A single layer film is made from the trimmed polypropylene having an MFR of 3 to 4g/10 min. Films were made on a 30:1 screw extruder with a 190HP AC driven 90mm slotted hole. The processing conditions used to produce the film included a 60 mil die opening gap, a 2.5BUR, and a melt temperature of 420 ° F (216 ℃) to 440 ° F (227 ℃).

Table 1 provides tPP resin as comparative example 1 (sample C1) and four samples produced by the methods described and discussed hereinExamples values for propylene compositions (samples 1-4). C1 is a control and contains only tPP resin. Samples 1 and 2 contained tPP resin and were commercially available from Milliken at 1,000ppm and 2,000ppm (relative to the amount of tPP) respectively&Of CompanyNX^TM8000 clarifying agent. Sample 3 contains tPP resin and 420ppm (relative to the amount of tPP used) of commercially available from Milliken&Of CompanyHPN-600ei nucleating agent. Sample 4 contained tPP resin and 150ppm (relative to the amount of tPP) of a commercially available resin from BASF, SEXT-386 clarifying agent.

The figure is a bar graph of secant flexural modulus (in machine and transverse directions) and haze and gloss values plotted for C1 and samples 1-4. These values are also given in table 1. For C1 and samples 1-4, the secant flexural modulus in the machine direction was 228,274 psi; 219,284 psi; 251,857 psi; 251,695 psi; and 251,374 psi. The polypropylene compositions of samples 2-4 had a greater secant flexural modulus in the machine direction than the control (C1). The secant flexural modulus in the transverse direction was 214,439psi for C1 and samples 1-4, respectively; 202,815 psi; 231,121 psi; 254,746 psi; and 234,899 psi. The polypropylene compositions of samples 2-4 had a greater secant flexural modulus in the transverse direction than the control (C1). The haze was measured to be greater than 30% for C1 and sample 1, but was measured to be 9%, 12%, and 12% for samples 1-3, respectively, as determined by ASTM D1003. For C1 and samples 1-4, the gloss at 45 ° in the machine direction was measured as 15, 12, 58, 47, and 46, respectively, as determined by ASTM D2457.

1% secant flexural modulus determined by secant/tensile as follows:

the equipment used was: a combined six (6) station, 60 degree machine contains the following:

the load frame test console contains an electrically driven crosshead mounted for horizontal motion. Opposite the crosshead, six (6) separate load cells were installed. These load cells are tension load cells.

Units #1 and #3 had a load cell ranging from 0-35 pounds. Unit #2 had a load cell ranging from 0-110 lbs. Each load cell is equipped with a set of pneumatic jaws (jaw). Each jaw has a face designed to create a line grip. The jaws combine a standard flat rubber face and an opposing face from which a metal half-circle extends. Cell #1 and #3 had 1 jaw 1/4 "wide, and cell #2 had 2 jaws 1/4" wide. Secant modulus was tested only on units #1 and # 3.

Preparing a sample: samples were conditioned and tested under ASTM laboratory conditions. They were maintained at 23. + -. 2 ℃ and 50% + 10% relative humidity. The conditioning time was a minimum of 40 hours under laboratory conditions and 48 hours after manufacture. 12 samples of each material were prepared: 6 in the Machine Direction (MD), i.e. the direction of flow as the polymer exits the die, and 6 in the Transverse Direction (TD), i.e. the direction perpendicular to the direction of flow as the polymer exits the die.

Note that: it is recommended that only 0-3 mils of material should be tested on units #1 and #3, and that all material thicknesses can be tested on unit # 2. But note that oriented PP measuring 0.7 mils can be loaded up to 35 lb. When testing unfamiliar materials, reminders and observations of the load were used.

Each sample should be 1 "wide and 7" long. The width (1 ") of the sample should be cut with a JDC precision, fixed blade cutter. These cutters are used because cuts or cuts in the sample can initiate premature breakage. After cutting each specimen, visual inspection was performed to ensure the edges were undamaged (no nicks). The owner of the cutter will periodically monitor the edge quality of the specimen by microscopic examination.

Testing information: secant modulus: (based on ASTM-D882-10)

Test templates currently in use: (template #) and test methods are as follows:

(5) 1% secant modulus Properties of films-ORG (units #1 and #3 only)

(9) 1% and 2% secant modulus Properties of the film-ORG (units #1 and #3 only)

(14) 1% and 5% secant modulus Properties of the film-ORG (units #1 and #3 only)

The film manufacturing process, density, resin grade, resin type and thickness all affect the test data. Stiffness properties were determined based on ASTM D882-10. These methods used 5 inch apart jaws and 1 inch wide samples. The stiffness index of the film was determined by pulling the sample at a jaw separation rate (cross-head speed) of 0.5 inches/minute to a specified strain of 1%, or 1% and 2%, or 1% and 5% of its initial length and recording the load at these points.

In summary, the polypropylene compositions of the present disclosure provide high melt strength, which can provide blown films having high melt strength, high gloss and low haze values.

As used herein, "consisting essentially of …" means that the claimed polymer or composition includes only the listed components, and does not have additional components that would alter its measured properties by no more than 10 or 20%; and most preferably means that additional components or "additives" are present to a level of less than 5, or 4, or 3, or 2 weight percent of the weight of the composition. Such additives may include, for example, fillers, colorants, antioxidants, alkyl-radical scavengers, UV-resistant additives, acid scavengers, slip agents, curing and crosslinking agents, oligomers or polymers containing aliphatic and/or cyclic groups (also known as "hydrocarbon resins"), and other additives known in the art.

To the extent not inconsistent herewith, all documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures.

Certain embodiments and features are described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges including any combination of two values, e.g., any lower value with any upper value, any combination of two lower values, and/or any combination of two upper values, are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below.