WO2018129115A1

WO2018129115A1 - Polyorganosiloxane and polyolefin blend composition in drawn polymer products

Info

Publication number: WO2018129115A1
Application number: PCT/US2018/012283
Authority: WO
Inventors: Jake H. MULLIGAN; John F. Steffen; David L. BYE
Original assignee: Great Lakes Polymers Holdings Corporation Dba Great Lakes Polymer Technologies
Priority date: 2017-01-04
Filing date: 2018-01-04
Publication date: 2018-07-12

Abstract

The present technology is directed towards a composition comprising a polyorganosiloxane and polyolefin blend. The composition may be included in the manufacture of extruded products, including those that have been oriented in the primarily in the machine direction. The extruded products include improved mechanical characteristics relative to the same compositions without the polyorganosiloxanes. These extruded products may include fibers, tapes, and extruded films for use in various construction and agricultural products.

Description

TITLE

POLYORGANOSILOXANE AND POLYOLEFIN BLEND COMPOSITION IN DRAWN POLYMER PRODUCTS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit from Provisional Patent Application No. 62/442,169 titled "POLYORGANOSILOXANE AND POLYOLEFIN BLEND COMPOSITION IN DRAWN POLYMER PRODUCTS" filed on January 4, 2017 which is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a composition for use in preparing polymer products, and more specifically, to a polyorganosiloxane and polyolefin blend composition for use in drawn polymer products.

BACKGROUND

[0003] Polymer products are widely used in a number of commercial applications, including fibers, tapes, and extruded films. The uses for these polymer products, however, can be limited based on their mechanical properties, including tensile strength, elongation, tenacity and modulus. The polymer products currently available in the marketplace are further limited by their processability issues and power consumption of their manufacturing lines.

[0004] Accordingly, there is a need to develop an improved polymer product for use to create a drawn product with improved mechanical properties, including tensile strength, elongation, tenacity and modulus.

SUMMARY

[0005] The present technology generally relates to a composition including a blend of polyorganosiloxanes and polyolefins (e.g., polyethylene, polypropylene, and blends thereof). When the polyorganosiloxane and polyolefin blend is added into the formulation for extruded products that will be oriented (i.e., drawn) primarily in the machine direction, the resulting products yield substantial benefits. In some embodiments, these extruded products may include fibers, tapes, and films (e.g., cast and blown films).

[0006] These benefits in extruded products containing a polyorganosiloxane and polyolefin blend include improvements in mechanical characteristics. The improved mechanical characteristics include, but are not limited to, higher tensile strength, increased elongation, higher tenacity, and/or increased modulus. The combination of benefits and their relative magnitudes may depend on the type(s) of polyolefin present in the composition, but may be more substantially impacted by the type of polyorganosiloxane (primarily dimethylsiloxane homopolymers (PDMS) and copolymers, and combinations of any two or more thereof), the fraction of polyorganosiloxane component in the overall composition, and the degree of orientation of the product (i.e., the draw ratio).

[0007] The polyorganosiloxane and polyolefin blend may be included in a variety of products, including, but not limited to, concrete products, agricultural netwrap products, twine products, strapping, and other known drawn tape applications, and the resulting products all exhibit improved mechanical characteristics.

[0008] In an embodiment, the present technology discloses a composition having a polyorganosiloxane and polyolefin blend, wherein the amount of polyorganosiloxane ranges from about 0.1 % w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition.

[0009] The composition may include an additive that makes up about 0% w/w to about 10% w/w of the composition. The additive may be a pigment, a light stabilizer, an antioxidant, a reinforcement particle, or a combination of two or more thereof.

[0010] In an embodiment, the present technology discloses a method of manufacturing a polyorganosiloxane and polyolefin blend composition. The method includes preparing a polyolefin ranging from about 50% w/w to about 99.9% w/w of the composition and adding a polyorganosiloxane, in an amount ranging from about 0.1 % w/w to about 50% w/w of the composition.

[0011] The polyorganosiloxane added may be added via a melt additive. The polyorganosiloxane may be added via a liquid feed process.

[0012] In an embodiment, the present technology may disclose an extruded product including a polyorganosiloxane and polyolefin blend composition, wherein the amount of polyorganosiloxane ranges from about 0.1% w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition and a construction material. [0013] The construction material may be asphalt or concrete. The extruded product may exhibit enhanced strength, enhanced modulus values and/or increased elongation values.

[0014] In an embodiment, the present technology may disclose an extruded product including a polyorganosiloxane and polyolefin blend composition, wherein the amount of polyorganosiloxane ranges from about 0.1% w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition and an agricultural material.

[0015] The agricultural material may be twine or netwrap. The extruded product may exhibit enhanced strength, enhanced modulus values and/or increased elongation values.

DETAILED DESCRIPTION

[0016] Reference will now be made in detail to exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings. It is to be understood that other embodiments may be utilized and structural and functional changes may be made without departing from the respective scope of the invention. Moreover, features of the various embodiments may be combined or altered without departing from the scope of the invention. As such, the following description is presented by way of illustration only and should not limit in any way the various alternatives and modifications that may be made to the illustrated embodiments and still be within the spirit and scope of the invention.

[0017] The present technology discloses a polyorganosiloxane and polyolefin blend composition. The composition may be added into the formulation for extruded products, including fibers, tapes, and films, thereby improving the mechanical characteristics of products that have been oriented/drawn primarily in the machine direction.

[0018] In an embodiment, the composition has a polyolefin component. Any appropriate amount of polyolefin may be used in the composition. In an embodiment, the amount of polyolefin component may range from about 50% w/w to about 99.9% w/w; from about 70% w/w to about

98% w/w; from about 60% w/w to about 97% w/w; from about 80% w/w to about 96% w/w; from about 90% w/w to about 95% w/w; and even from about 91 % w/w to about 94% w/w of the composition. In an embodiment, the amount of polyolefin component may be 97% w/w of the composition. In an embodiment, the amount of polyolefin may be about 97.5% w/w of the composition. In an embodiment, the amount of polyolefin may be about 90% w/w to about 99% w/w of the composition. The polyolefin component may be selected from any appropriate polyolefin, including, but not limited to, polypropylene (homopolymers and/or copolymers), polyethylene (homopolymers and/or copolymers, such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc.) polybutadiene, and other polyalphaolefins, or combinations of any two or more thereof. In an embodiment, the polyolefin composition may be primarily made of polypropylene. In an embodiment, the polyolefin composition may be primarily made of polypropylene blends wherein the primary constituent is polypropylene. In an embodiment, these blends may also include other non-poly olefins.

[0019] Any appropriate amount of polyorganosiloxane may be used in the composition. In an embodiment, the polyorganosiloxane component may be present in an amount ranging from about 0.1 % w/w to about 50% w/w of the composition. In an embodiment, the polyorganosiloxane component may range from about 0.5% w/w to about 10% w/w; from about 1 % w/w to about 5% w/w; or even from about 2% w/w to about 4% w/w of the composition. In an embodiment, the polyorganosiloxane component may be approximately 0.5% w/w of the composition. In an embodiment, the polyorganosiloxane component may be approximately 1% w/w of the composition.

[0020] The polyorganosiloxane and polyolefin blend composition may also include additional components, such as additives. These additives may include, but are not limited to, light stabilizers and antioxidants. The composition may also include pigments, reinforcement particles, and other similar components. Any appropriate amount of additives may be used in the composition. In an embodiment, the amount of additive component present in the composition may range from about 0% w/w to about 10% w/w; from about 0.5% w/w to about 5% w/w; and even from about 1 % w/w to about 3% w/w of the composition. In an embodiment, the additive component may be approximately 2% w/w of the composition.

[0021] In one method of preparing the polyorganosiloxane and polyolefin blend composition, a polyorganosiloxane is added as a melt additive in pellet form into a standard hopper system feeding an extruder. Other methods of manufacture may be used, e.g., liquid feed.

[0022] The polyorganosiloxane and polyolefin blend composition may be added to various material compositions to improve the mechanical properties of the resulting materials. For example, the polyorganosiloxane and polyolefin blend composition may be added into construction products, including, but not limited to, concrete fibers, asphalt fibers, etc. Additionally, the polyorganosiloxane and polyolefin blend composition may be added to agricultural products including, but not limited to, twines, netwrap, etc. Furthermore, the polyorganosiloxane and polyolefin blend composition may be added to strapping, and other known drawn tape applications.

[0023] The inclusion of the polyorganosiloxane and polyolefin blend composition enhances the performance of finished products, including, but not limited to, strength, tenacity, modulus, and elongation. The enhancements depend in part on the types of polyolefin present in the composition, as well as the type of polyorganosiloxane (e.g., dimethylsiloxane homopolymers (PDMS) and copolymers, and combinations of any two or more thereof), the fraction of polyorganosiloxane component in the overall composition, and degree of orientation of the end production (i.e., the draw ratio).

[0024] The strength of the finished product may be enhanced and either increased or decreased depending on the desired outcome for the product's use. A controlled reduction is possible, particularly at lower draw ratios. For example, the addition of polyorganosiloxane to a composition allows for the control of the strength of a finished product. The strength may be decreased by as much as 33%, depending on the addition of polyorganosiloxane, the type of polymer into which it is blended, and the extent to which the extruded product is drawn/stretched. In an embodiment, the strength of the finished product may be increased through the addition of polyorganosiloxane. In an embodiment, the strength may be increased from about 5% to about 75%, from about 10% to about 65%, from about 20% to about 55%, and even from about 30% to about 45%. In an embodiment, the strength of the finished product containing polyorganosiloxane may be increased from about 5% to about 25%.

[0025] The tenacity of the finished product may be enhanced and either increased or decreased depending on the desired outcome for the product's use. A controlled reduction of tenacity is possible. While not always desirable, the addition of polyorganosiloxane to a composition allows for the control of the tenacity of a finished product. The tenacity may be decreased by as much as 33%, depending on the addition of polyorganosiloxane. In an embodiment, the tenacity of the finished product may be increased through the addition of polyorganosiloxane, the type of polymer into which it is blended, and the extent to which the extruded product is drawn/stretched. The tenacity of the finished product may show a greater improvement when added to polypropylene and polypropylene blends. In an embodiment, the tenacity may be increased from about 1% to about 100%, from about 3% to about 80%, from about 5% to about 60%, from about 7% to about 40% and even from about 10% to about 20%. In an embodiment, the tenacity of the finished product containing polyorganosiloxane may be increased from about 5% to about 33%.

[0026] The modulus of the finished product may be enhanced and either increased or decreased depending on the desired outcome for the product's use. A controlled reduction of the modulus is possible. That is, the addition of polyorganosiloxane to a composition allows for the control of the modulus of a finished product. The modulus may be decreased by as much as 67%, depending on the addition of polyorganosiloxane. In an embodiment, the modulus of the finished product may be increased through the addition of polyorganosiloxane, the type of polymer into which it is blended, and the extent to which the extruded product is drawn/stretched. The modulus of the finished product may show a greater improvement when added to polypropylene and polypropylene blends. In an embodiment, the modulus may be increased from about 1% to about 100%, from about 3% to about 80%, from about 5% to about 60%, from about 7% to about 40% and even from about 10% to about 20%. In an embodiment, the modulus of the finished product containing polyorganosiloxane may be increased from about 5% to about 50%. In an embodiment, the modulus may be doubled.

[0027] Further, the elongation of the extruded product may be increased through the addition of polyorganosiloxane. Depending on the amount of polyorganosiloxane added, the type of polymer into which it is blended, and the extent to which the extruded product is drawn/stretched, the elongation value will vary. The elongation of the finished product may show a greater improvement when added to polypropylene and polypropylene blends. In an embodiment, the elongation may be increased from about 1% to about 500%, from about 5% to about 300%, and even from about 10% to about 200%. In an embodiment, the elongation value may increase by about 10% to about 100%.

[0028] Further, the enhancement of elongation values allows for higher draw ratios, and thus, orientation, during processing. The result of which may be an extruded product with a higher tensile strength, higher modulus, and greater tenacity, while still retaining a higher elongation in application when compared to identical compositions without polyorganosiloxanes when the compositions are stretched to the same draw ratio and degree of orientation.

[0029] The addition of other materials to the composition may also help to increase intrinsic elongation, thereby allowing for an increased draw ratio and enhancement of mechanical characteristics in a similar way. In an embodiment, the polyorganosiloxane and polyolefin blend composition may also include other materials that will allow for the same benefits as the addition of polyorganosiloxane. For example, the addition of elastomers and plastomers, including, but not limited to, polyolefin plastomers and elastomers, styrene-butadiene block copolymers, styrene-isoprene block copolymers, polyester block copolymers, and combinations of any two or more thereof. These materials may be added in any appropriate amount, but may require addition at about 1% w/w to 25% w/w to achieve similar benefits to the addition of polyorganosiloxane to the same composition at about 0.1% w/w to about 10% w/w. The resulting product may have an increased draw ratio and other enhanced mechanical characteristics.

[0030] As discussed above, the polyorganosiloxane and polyolefin blend composition may be added into construction products, including, but not limited to, concrete fibers, asphalt fibers, etc. During manufacture, the polyorganosiloxane and polyolefin blend composition is prepared as described above. The resulting concrete fibers/filaments are cut into any appropriate sized pieces, e.g., 2.0 inches or less. In an embodiment, the concrete fibers/filaments may be any appropriate sized pieces greater than or equal to 2.0 inches, e.g., 54 or 60 mm. The concrete fibers/filaments are then added into the mixing concrete. The resulting product is a reinforced concrete product that experiences less cracking and reduced impact of cracking that still occurs. Asphalt fibers are manufactured in a similar manner. The construction product exhibits at least increased tensile strength, increased elongation to break, increased tenacity, and increased modulus.

[0031] As discussed above, the polyorganosiloxane and polyolefin blend composition may be added into agricultural products, including, but not limited to, netwraps, twines, etc. During manufacture, the polyorganosiloxane and polyolefin blend composition is prepared as described above and further manufactured into approximately sized and dimensioned netwrap and/or twine. The resulting agricultural product exhibits at least increased tensile strength, increased elongation, and increased tenacity.

[0032] The products may also achieve increased toughness which may result in increased durability. If the increased toughness results in difficulty cutting the product, modifications to cutting equipment may easily overcome any issues. Further benefits of the technology include chemical resistance and resistance to ultraviolet light and other forms of radiation as polyorganosiloxanes are intrinsically chemical and radiation-resistant materials. Further, the products may include increased improvements to processability including, but not limited to, power draw, film stability, and reduced die build-up.

[0033] When products were compared with equivalent orientation (i.e., the drawing process was maintained as constant), multiple benefits exist. First, the elongation of the final product increased. Second, the modulus of the final product increased, depending on the type of polyorganosiloxane used. Lastly, there is an increased processability improvement, including, but not limited to, increased stability of the process, e.g., fewer instances of the manufacturing line going down for the operator to restring the line, as with the addition of polyorganosiloxane to the composition, the problem is reduced or even eliminated. Further, the power consumption for manufacturing may be reduced by approximately 1% to approximately 50%. In an embodiment, the power consumption for manufacturing may be reduced by approximately 15%.

[0034] The following examples are intended to illustrate, but in no way limit, the scope of the present technology.

EXAMPLES

Example 1

[0035] A control composition was prepared with polypropylene and additives, i.e., similar to the compositions currently available in the market. Sample # 1 was the same formulation as the control except that a small fraction of the polypropylene was replaced such that the final composition would have 0.5% w/w polyorganosiloxane, which was introduced as part of a 50/50 masterbatch combination of polyorganosiloxane and polypropylene premix. The resulting composition of Sample #1 is made of the same additives along with 0.5% w/w LDR polyorganosiloxane. Sample #2 was the same formulation as the control except that a small fraction of the polypropylene was replaced such that the final composition would have 1% w/w polyorganosiloxane, which was introduced as part of a 50/50 masterbatch combination of polyorganosiloxane and polypropylene premix. The resulting composition of Sample #2 is made of the same additives along with 1% w/w LDR polyorganosiloxane. The control, Sample #1 and Sample #2 compositions all underwent the same preparation. All three compositions were extruded in the same manner at the same temperature profile, and then cooled in the same water bath at the same temperature, drawn to the same draw ratio in an oven that was maintained at the same temperature throughout the Example 1 experiment, and were all taken up onto spools in the same standard manner. Each data point presented in Table 1 below is an average of the ten samples prepared for each composition.

Table 1. Mechanical Properties of Fiber Containing a

Pol or anosiloxane and Pol olefin Blend Com osition

Example 2

[0036] Samples of twine containing the polyorganosiloxane and polyolefin blend composition were prepared. The samples were produced with 98% 4 MFR homopolymer polypropylene and 2% additive masterbatches which included UV stabilizers, colorants and antioxidants. The two inventive samples contained 96% 4 MFR homopolymer polypropylene and 2% additive masterbatch (UV stabilizers, color and antioxidants). The material was blended in a hopper system and fed to an extruder. The molten polymer was cast into a film and cooled on a chilled roll and slit into thick tapes. The thick tapes were subsequently drawn through an oven at the same draw ratio and temperature for each condition. The oriented tapes were then twisted into twine at the same conditions to yield the control and inventive products. Each data point presented in Table 2 below is an average of the 10 tests for samples prepared for each composition. Table 2. Mechanical Properties of a Twine Product

[0037] From the foregoing, it will be observed that numerous modifications and variations can be affected without departing from the true spirit and scope of the novel concept of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated herein is intended or should be inferred. The disclosure is intended to cover, by the appended claims, all such modifications as fall within the scope of the claims. Although the embodiments of the present invention have been illustrated in the accompanying drawings and described in the foregoing detailed description, it is to be understood that the present invention is not to be limited to just the embodiments disclosed, but that the invention described herein is capable of numerous rearrangements, modifications and substitutions without departing from the scope of the claims hereafter. The claims as follows are intended to include all modifications and alterations insofar as they come within the scope of the claims or the equivalent thereof.

Claims

CLAIMS Having thus described the invention, the following is claimed:

1. A composition comprising:

a polyorganosiloxane and polyolefin blend, wherein the amount of polyorganosiloxane ranges from about 0.1 % w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition.

2. The composition of claim 1 , wherein the composition further comprises an additive.

3. The composition of claim 2, wherein the additive comprises about 0% w/w to about 10% w/w of the composition.

4. The composition of claim 2, wherein the additive is selected from the group consisting of: a pigment, a light stabilizer, an antioxidant, a reinforcement particle, or a combination of two or more thereof.

5. A method of manufacturing a polyorganosiloxane and polyolefin blend composition comprising:

preparing a polyolefin ranging from about 50% w/w to about 99.9% w/w of the composition; and

adding a polyorganosiloxane, in an amount ranging from about 0.1% w/w to about 50% w/w of the composition.

6. The method of claim 5, wherein the polyorganosiloxane is added via a melt additive.

7. The method of claim 5, wherein the polyorganosiloxane is added via a liquid feed process.

8. An extruded product comprising:

a polyorganosiloxane and polyolefin blend composition, wherein the amount of polyorganosiloxane ranges from about 0.1% w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition; and a construction material.

9. The product of claim 8, wherein the construction material is asphalt.

10. The product of claim 8, wherein the construction material is concrete.

1 1. The product of claim 8, wherein the extruded product exhibits enhanced strength.

12. The product of claim 8, wherein the extruded product exhibits enhanced modulus values.

13. The product of claim 8, wherein the extruded product exhibits increased elongation values.

14. An extruded product comprising: a polyorganosiloxane and polyolefin blend composition, wherein the amount of polyorganosiloxane ranges from about 0.1% w/w to about 50% w/w of the composition, and the amount of polyolefin ranges from about 50% w/w to about 99.9% w/w of the composition; and an agricultural material.

15. The product of claim 14, wherein the agricultural material is twine.

16. The product of claim 14, wherein the agricultural material is netwrap.

17. The product of claim 14, wherein the extruded product exhibits enhanced strength.

18. The product of claim 14, wherein the extruded product exhibits enhanced modulus values.

19. The product of claim 14, wherein the extruded product exhibits increased elongation values.