JP4545141B2 - Extrudable PVC composition - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is based on and claims the priority of US Provisional Application No. 60 / 445,492, filed Feb. 6, 2003, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION Extrusion of a thermoplastic material such as polyvinyl chloride (PVC) generally heats the extrudable mixture to a temperature at which it can cause a plastic flow and then one or more thereof. It needs to be pushed through a plate containing an orifice opening (sometimes called a die) to give the extruded product a profile shape. The extrudate is then cooled until it is hard enough to retain the profile shape.

  In general, extruded feed compositions are made by mixing a thermoplastic polymer, such as a PVC resin, with one or more adjuvants, such as a lubricant. For example, extrudable PVC compositions are described in Handbook of Plastic Material and Technology, Ed. I. Rubin, Wiley-Interscience, John Wiley & Sons, Inc. New York, 1990 and Plastics, each incorporated herein by reference. Additives and Modifiers Handbook, Ed. J. Edenbaum, Van Nostrand Reinhold, New York 1992, Chapter 3. Examples of additional ingredients include fillers such as calcium carbonate; processing aids such as acrylic copolymers; and stabilizers that provide thermal stability to the composition during the extrusion process, such as TM281 from Rohm & Haas ( Tin-based stabilizers such as registered trademark). The composition is then generally "melted", ie, heated and blended until it forms a plastic composition that is substantially uniform. The various additives and the amount of additive used will affect the properties of the extrudable composition both during the melting process and after it has been “melted”. Those properties of the composition, in turn, affect performance, such as the processability of the material during extrusion or subsequent processing in which the extruded material is used. Of the various components that make up a typical extrudable PVC composition, the lubricants included in the composition can contribute to one or more properties related to processability and to the quality of the extrudate. Can have significant impact. Standards for properties and performance of thermoplastic extrudates are, for example, ASTM Standard D3679-03e2 for PVC slats and D1785-03 for PVC pipes, as well as for impact resistant PVC profiles for windows and doors. DIN Standard 16830-3 is well known.

  Dimensional stability is an important property that affects the commercial value of the extruded product, and thus the commercial value of the methods and ingredients used to produce the extruded product. Dimensional stability is assessed by observing how much the extruded shape expands during solidification after it exits the die of the extruder. The amount of expansion is sometimes referred to as die swell.

  For a given extrudable composition, it is generally possible to increase the amount that the material is extruded. However, such an increase in the amount of extrusion has a practical limit. For example, obtaining an increase in extrusion volume is possible by operating the extruder at a higher temperature and / or with a higher head pressure. However, at some point in increasing extruder temperature, the extrudable composition will generally begin to scorch and the quality of the extrudate surface and structure will begin to decline. Furthermore, as head pressure and extruder torque increase, the dimensional stability and / or surface condition of the extruded material generally reaches an unacceptable point. These process limits have created practical limits on the amount that conventional compositions can be extruded.

  Another mechanism that is at least theoretically available to achieve higher extrusion rates is to increase the amount and / or type of lubricant incorporated into the extrudable composition. However, it is also conceivable that increasing the amount of lubricant or changing the lubricant type may have deleterious effects on the extruded product and / or other aspects of the extrusion process. For example, increasing the amount of certain lubricants known as internal lubricants may affect one or more inherent physical properties of the extrudate, such as reducing the tensile strength of the extrudate. . Furthermore, the increased amount of external lubricant can not only negatively affect the strength of the extrudate, but can also increase the melting time, which increases the overall process time.

  Accordingly, Applicants are believed to have one or more desirable extrusion properties associated with extrudable compositions, specifically high levels of lubricants, while at the same time being associated with high levels of lubricants. A need has been realized for an extrudable PVC substrate composition that reduces or substantially eliminates one or more adverse effects. The present method and extrudable composition meet this and other needs.

SUMMARY OF THE INVENTION One aspect of the present invention is an extrudable composition, more preferably a thermoplastic polymer such as polyvinyl chloride and at least one polysaccharide ester, preferably a dipolyester, and even more preferably, An extrudable composition comprising a sucrose ester is provided. Applicants have discovered that such compositions can exhibit property combinations that are highly desirable but difficult to obtain. For example, in some preferred embodiments, the extrudable composition can exhibit desirable low internal viscosity values, and / or other properties that are generally favorable and / or desirable for the extrusion properties of the composition, At the same time, it can be extruded into a solid having desirable properties such as relatively high tensile strength and / or relatively high dimensional stability.

Another aspect of the invention involves a method of extruding a thermoplastic composition, preferably a polyvinyl chloride base composition. The method is preferably
(A) providing an extrudable thermoplastic material comprising at least one thermoplastic polymer and at least one polysaccharide ester, preferably sucrose ester; and (b) extruding the extrudable material to form a shaped article Including doing. The polysaccharide ester preferably has an extrudability of the extrudable material in its composition, preferably at least about 10%, more preferably compared to the extrudability of the extrudable material in the absence of the polysaccharide ester. Is present in an amount effective to improve at least about 20%, even more preferably at least about 30%. The extrudability of an extrudable material can be measured by any one of several properties of the extrudable material, as described in detail below.

According to another aspect of the present invention, a shaped article is provided and / or molded using the extrudable composition and / or extrusion method of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Although it is contemplated that the present invention will have the greatest applicability in connection with the extrusion of thermoplastic polymers, it will also have applicability to other extrudable compositions. It's thought to be. For example, ram extrusion of polymers that are not strictly thermoplastic, such as polytetrafluoroethylene (PTFE), can be beneficially affected by the present invention. Thus, the term “extrudable composition” as used herein means not only a composition containing a thermoplastic polymer, but also is easily extrudable by known techniques, or otherwise. It is also used to mean a polymer that behaves similarly to a thermoplastic polymer with respect to the extrusion process. Such extrudable polymers, whether thermoplastic or otherwise, are sometimes referred to herein as resins for convenience.

Method In one aspect, the present invention relates to a method of forming a shaped article from an extrudable composition. In general, the first step is to provide an extrudable composition according to the present invention. While it is contemplated that the extrudable composition of the present invention can be provided by any means known in the art, generally the extrudable composition comprises at least a resin and a polysaccharide of the present invention. Suitably the ester is formed by mixing under conditions effective to form an extrudable composition. As is known in the art, the requirements for extrudable compositions vary widely, particularly depending on the equipment used and the desired extrudate properties, but all such extrudable compositions. Things are within the scope of the present invention. Generally, these conditions include mixing the mixed resin, polysaccharide ester, and one or more other ingredients that may be present. Preferably, the blending process generates shear heat within the composition, but the combination of shear and heat softens and melts the individual particles of the composition, resulting in a substantially uniform material. At the point of melting (melting point), the integrity of the individual granules in the composition is preferably substantially lost.

  When such heating and blending is performed under known standard test conditions, the blending time required to reach the melting point is referred to as “melting time”. Generally, at the melting point, the viscosity of the composition is a maximum, but at about this same point, the torque required to blend the materials will be the maximum. The torque maximum is related to melt viscosity and is reported as melt torque. It is believed that with continued blending, the viscosity of the composition and the torque required to blend the composition will decrease to a relatively steady state condition. The steady state value is referred to as the equilibrium viscosity, the temperature of the composition at this point is referred to as the equilibrium temperature, and the torque required to blend the composition at this point is referred to as the equilibrium torque. With continued blending, the composition is believed to begin to crosslink, and the viscosity of the composition begins to increase, and therefore, the blend torque is expected to begin to increase. The elapsed time between the melting point and the start of a measurable viscosity increase due to crosslinking is referred to as the stabilization time.

  The method of the present invention then involves extruding the provided extrudable composition to form a shaped article. Preferably, the extruding process includes bringing the extrudable composition of the present invention to a temperature at which it can undergo plastic flow. In a preferred embodiment, this involves heating the extrudable composition and pressing the extrudable composition through a die containing one or more openings to deform the exiting extrudate. Including providing a material shape.

  One important property of the method and the technique that can be used to measure extrudability is related to the amount of force required to push the composition through the die. In general, the step of pushing the extrudable composition through the die by the present method is advantageously compared to other methods that can produce an extrudate of a quality comparable to that which can be produced by the present invention. Requires a relatively small amount of force. Preferably, the polysaccharide ester has the force required to push the extrudable material through the die into the composition under all other conditions that are substantially the same except for the absence of the polysaccharide ester. Present in an amount effective to reduce by at least about 10%, more preferably at least about 20%, even more preferably at least about 30% compared to the force required to push the extrudable material through the die. To do.

  Applicant is not intending to be bound by or to any particular theory of operation, but that the presence of a polysaccharide ester in a suitable extrudable composition of the present invention provides the benefits of both internal and external lubricants. At the same time, it is believed to avoid the adverse effects often associated with internal and external lubricants. An “internal lubricant” is believed to affect the processability of the composition by reducing the cohesive force that imparts viscosity to the composition. By reducing these forces, it is believed that the polymer molecules that make up the bulk of the composition can more easily “slip” away from each other when pressure is applied. In this manner, the polysaccharide esters of the present invention preferably result in a reduction in the apparent viscosity of the extrudable composition, which is another measure of extrudability. Accordingly, in some embodiments, the polysaccharide ester has an apparent viscosity of the composition in the composition at all other conditions that are substantially the same except for the presence of the polysaccharide ester. It is present in an amount effective to reduce by at least about 10%, more preferably at least about 20%, and even more preferably at least about 30% compared to the viscosity.

  Preferred extrudable compositions of the present invention require relatively less force to impart plastic flow to the composition. The method of the present invention can thus provide an extrusion process using a relatively low head pressure and a relatively low torque required to drive the extrusion process, each of which is extrudability of the material. It is also a characteristic that can be measured. In some embodiments, the polysaccharide ester preferably compares the head pressure in its composition to the head pressure required in all other conditions that are substantially the same except for the presence of the polysaccharide ester. It is present in an amount effective to reduce by at least about 10%, more preferably by at least about 20%, and even more preferably by at least about 30%. Further, in some embodiments, the polysaccharide ester has an extrusion torque in its composition that is at least compared to the extrusion torque required in all other conditions that are substantially the same except for the presence of the polysaccharide ester. It is preferred that it be present in an amount effective to reduce by about 10%, more preferably by at least about 20%, and even more preferably by at least about 30%.

  The preferred method of the present invention can thus yield an extruded product with greatly improved dimensional stability. Preferably, the polysaccharide ester has a dimensional stability of the extruded product in its composition compared to the dimensional stability of the extruded product at all other conditions that are substantially the same except for the presence of the polysaccharide ester. It is present in an amount effective to increase by at least about 10%, more preferably by at least about 20%, and even more preferably by at least about 30%. Once again, Applicant is not intending to be bound by or to any particular theory, but to impart plastic flow to the extrudable material of the present invention, whether in the form of heat and / or pressure, Since less energy is required, it is believed that the compositions and methods of the present invention can achieve this desirable result. Importantly, preferred embodiments of the present invention provide this advantageous reduction in extrusion energy, which is an indicator of improved extrudability, without any substantial sacrifice or reduction in dimensional stability in the extruded product. And more preferably, achieved without any substantial reduction in tensile strength. Dimensional stability is assessed by observing how much the extruded shape expands during solidification after it exits the die. Such expansion is sometimes referred to as die swell. The relatively low extrusion temperature can be used with the preferred method of the present invention so that the extruded material solidifies more rapidly after leaving the die. In addition, the preferred method of the present invention allows the use of relatively low extrusion pressures, thereby resulting in a reduction in residual resiliency in the exiting extrudate. The reduction in the amount of energy that must be consumed by the expansion of the material as it exits the die is believed to appear as a desirable reduction in die swell.

  Without being bound by or with any particular theory, the polysaccharide esters of the present invention may further comprise, for example, a die and an extrudable composition at the interface between the composition and the surface in contact with the composition. It is thought to act as an external lubricant at the point of contact between This in turn reduces the force required to overcome the flow resistance through the conduit or orifice, and further beneficially improves the quality of the extrudate surface, such as increased surface smoothness of the extrudate. To do. The quality of the extrudate surface is typically assessed by measuring its reflectivity (gloss). For example, ASTM standards D-2523-95 and D2457-97 are known for measuring gloss. Preferably, the polysaccharide ester has at least about a gloss of the extruded product in its composition compared to the dimensional stability of the extruded product at all other conditions that are substantially the same except for the presence of the polysaccharide ester. It is present in an amount effective to increase by 10%, more preferably by at least about 20%, and even more preferably by at least about 30%.

  As the extrudate exits the orifice opening, it is preferably cooled to yield a relatively rigid product having the basic shape provided by the die. The shaped extrudate is in one of its extruded forms, for example, as a decorative molded product, as a fence member, as a building siding, as a pipe, as a conduit, as a window member, as a door Although it can be used as a frame, as a skirting board, as a rain gutter and similar products, all such products produced by this method or using the present composition are within the scope of the present invention. The extrudate can be further cut and packaged into convenient length parts for use in subsequent processes, for example, as a feedstock for injection molding or blow molding processes.

  Thus, in a preferred embodiment, the method comprises at least one measure of extrudability of at least one polyvinyl chloride resin and a polysaccharide ester as compared to the properties of the same composition except in the absence of the polysaccharide ester and / or Providing an extrudable composition comprising an amount effective to improve the measure of extrudate quality. Preferably, the method of the present invention produces improvements in at least one measure of extrusion performance and in one measure of extrudate quality. More particularly, the method preferably exhibits improved performance in one or more of the following extrusion suitability criteria: extrusion torque; head pressure; and processing stability. The method more preferably results in extrudates exhibiting improvements in one or more of the following properties: surface gloss; dimensional stability; and tensile strength.

Compositions The present invention provides extrudable compositions, additive compositions useful in formulating extrudable compositions, and extruded compositions formed from the extrudable compositions of the present invention.

Extrudable compositions Preferred compositions of the present invention exhibit improved melting torque, equilibrium torque, melting time, equilibrium temperature and processing stability (dynamic thermal stability). As mentioned above, these properties will generally result in improved properties of the extrusion process. In other words, the inventor has the inclusion of polysaccharide esters, preferably sucrose esters, in the extrudable composition, preferably a composition comprising PVC, is substantially the same except for the lack of polysaccharide esters. Compared to the composition, improved dynamic stability, lower head pressure, lower melt torque, lower apparent viscosity, and improved dimensional stability and improved for extruded products made therefrom. It has been discovered that compositions that exhibit high surface gloss can be provided.

  In addition to resins and polysaccharide esters, the composition comprises impact modifiers, fillers, heat stabilizers, processing aids, other lubricants, fillers, binders, colorants, and other processing aids, For example, Handbook of Plastic Material and Technology, Ed.I.Rubin, Wiley-Interscience, John Wiley & Sons, Inc.New York, 1990 and Plastics Additives and Modifiers Handbook, Ed.J.Edenbaum, Van Nostrand Reinhold , New York 1992, Chapter 3 may be included.

Polysaccharide esters It is contemplated that all saccharide esters, including monosaccharides and disaccharides, may be suitable for use in connection with the present invention. In a preferred embodiment, the polysaccharide ester consists essentially of or comprises a dipolysaccharide ester, more preferably a polysaccharide ester of a fatty acid, even more preferably a dipolysaccharide ester of a fatty acid. Preferably, the fatty acid esters comprise saccharides, preferably sucrose, soybean oil, commercial behenic acid and commercial stearic acid (hereinafter sucrose “soyate”, sucrose “behenate” and sucrose “stearate”, respectively) and their Synthesized by esterification with one or more fatty acid moieties obtained from the group consisting of mixtures. Stearate esters can be synthesized by hydrogenating soyate esters. Preferably, suitable saccharide esters comprise a saccharide moiety, preferably a sucrose moiety, substituted with an ester moiety at one or more hydroxyl hydrogens. Suitable dipolysaccharide esters have the structure of formula I

Where “A” is hydrogen or the structure I below

Wherein “R” is a linear, branched or cyclic saturated or unsaturated aliphatic or aromatic moiety having from about 8 to about 40 carbon atoms.
Wherein at least one “A” to up to a total of eight “A” moieties of formula I follow structure I.

  Suitable “R” groups include any form of an aliphatic moiety, including those containing one or more substituents that may be on any carbon of the moiety. . Also included are aliphatic moieties that include functional groups within the moiety, such as ethers, esters, thios, aminos, or the like. Also included are oligomer and polymer aliphatic moieties such as sorbitan moieties, polysorbitan moieties and polyalcohol moieties. Examples of functional groups that may be attached to the aliphatic or aromatic moiety constituting the “R” group include, but are not limited to, halogen, alkoxy, hydroxy, amino, ether and ester functional groups. is not.

  In general, suitable dipolysaccharide esters are sucrose esters according to Figure I, wherein the "R" group is aliphatic, linear or branched, saturated or unsaturated, from about 8 to about 40 Has carbon atoms.

Most preferred are fatty acids in which the carboxyl group has from about 8 to about 25 carbon atoms, such as stearic acid (CH ₃ (CH ₂ ) ₁₆ C (O) OH), behenic acid (docosanoic acid, (CH ₃ ( CH ₂ ) ₂₀ C (O) OH)), and polysaccharide esters derived from fatty acids derived from soybean oil, preferably sucrose esters, but the final composition is more fully described below. Yes.

  As used herein, the terms “polysaccharide ester” and “sucrose ester” encompass compositions having different purities, as well as mixtures of compounds having any purity level. For example, a sucrose ester compound can be a substantially pure substance, that is, it can include a compound having a number of “A” groups substituted with a structure I moiety of only one species (ie, , All “R” groups are the same and all sucrose moieties are substituted to the same extent). It further includes compositions comprising a blend of two or more sucrose ester compounds that differ in the degree of substitution, but all substituents have the same “R” group structure. It further has a different degree of “A” group substitution, wherein the “R” group substituent moiety is independently selected from two or more “R” groups of structure I. Includes compositions that are mixtures of compounds.

  When a substantially pure compound is used for the composition of the present invention, the composition will preferably comprise a polysaccharide ester compound having a high degree of substitution, even more preferably a sucrose ester compound. Preferably, the mass above 70% by weight including the polysaccharide ester will include moieties that are fully substituted with ester groups.

  In general, it is believed that the degree of substitution with the R group at the A position in Formula I will strongly affect the properties imparted to the composition. That is, the number of protons (1-8) at the “A” position replaced by the portion of Structure II is considered important for one or more properties of the composition such as lubricity. In general, the performance improvement imparted to an extrudable PVC composition by a certain mass of additional polysaccharide ester will increase as a percentage by weight of the fully substituted sucrose ester including the mass increase.

  For use in the compositions of the present invention, a fully substituted dipolysaccharide ester, preferably a sucrose ester, precisely also referred to herein as an “octasubstituted” sucrose ester, sometimes for convenience. It is preferred to use a sucrose ester having 8 ester groups attached to the sucrose moiety. The inventor has observed that the beneficial effect that sucrose esters have on extrudable PVC compositions is maximized when the total amount of sucrose esters included in the composition is eight-substituted. This is because, for compositions containing a certain part by weight of sucrose ester relative to the part of resin present in the extrudable composition, preferably PVC resin, the improvement in the extrusion characteristics of the composition is generally That is, it increases as the degree of substitution increases. Furthermore, the inventor has shown that the beneficial effect imparted to the extrudable PVC composition by the addition of a certain weight of pure aliquot of less than fully substituted sucrose ester is that more and more additional ester aliquots are replaced. It was also observed that the inclusion increases in a non-linear manner, with a greater increase in the disparity observed for more fully substituted species. The beneficial effect on the extrudable PVC composition is maximized when using pure aliquots of fully substituted (octasubstituted) sucrose esters.

  When a mixture of sucrose ester compounds is used, more than about 50% by weight of the ester compound in the mixture is a fully substituted dipolysaccharide ester, ie all eight “A” groups of the disaccharide moiety are It is preferred to have a structure that includes a portion of structure I. In the compositions of the present invention, it is preferred that the components of the dipolysaccharide ester, preferably the sucrose ester, comprise more than about 70% by weight of fully substituted ester moieties.

  Factors to be considered when selecting a sucrose ester for inclusion in the extrudable PVC composition of the present invention include the length and saturation of the “R” group of the substituent moiety. Additional factors that may be considered include the compatibility of the sucrose ester with other lubricants that may be present in the composition, and the physical properties of the sucrose ester with the processing conditions used to make the extrudable PVC composition. Conformity of form is included. For example, it may be more convenient to treat sucrose esters that are solid rather than liquid under ambient conditions.

  Polysaccharide esters can be prepared by esterification with substantially pure fatty acids (eg, stearic acid that yields sucrose stearate) by known esterification methods. They can also be produced, for example, by transesterification with fatty acid esters and saccharides in the form of fatty acid glycerides derived from natural sources such as oils extracted from oilseeds, such as those found in soybean oil. it can. Transesterification reactions using fatty acid glycerides to provide sucrose esters are described, for example, in US Pat. No. 6,504,003 by Trout et al. And 6,121,440 by Kenneally et al. In the Trout patent, Example 1 is an ester in which 78% by weight of the product ester is octyl substituted (fully substituted), the remainder of the product being mono-, di-, tri-, tetra- A transesterification reaction is described which provides a sucrose ester comprising a distribution of substituted, pentasubstituted, hexasubstituted and heptasubstituted sucrose esters.

As mentioned above, sucrose esters can be produced by transesterification of sucrose from a methyl ester feedstock made from glycerides derived from natural sources. As a consequence of the fatty acid source, the feedstock used to produce the sucrose ester contains a range of saturated and unsaturated fatty acid methyl esters having a fatty acid moiety containing 12 to 26 carbon atoms. This will be reflected in product sucrose esters made from such sources in that the sucrose moieties that make up the product will contain a mixture of ester moiety substituents, Here, with respect to Structure I above, the “R” group will be a mixture having 12 to 26 carbon atoms in a ratio that reflects the feedstock used to produce the sucrose ester. To further illustrate this point, sucrose esters derived from soybean oil can be obtained as described in the Seventh Ed. Of the Merck Index, incorporated herein, so that 26% by weight of oleic acid is used in soybean oil. _{(H 3 C- [CH 2]} 7 -CH = CH- [CH 2] 7 C (O) OH) triglycerides, 49% by weight of linolenic acid _{(H 3 C- [CH 2]} 3 - [- CH 2 _{-CH = CH] 2 - [-} CH 2 -] triglycerides of 7 -C (O) OH), 11 wt% of linolenic acid _{(H 3 C - [- CH} 2 -CH = CH-] 3 - [- CH _2- ] ₇ -C (O) OH) triglycerides and 14% by weight of various saturated fatty acid triglycerides would reflect a mixture of species having an "R" group structure. All of these fatty acid moieties are shown in the “R” group of the substituent in the product sucrose ester. Thus, when discussing herein sucrose esters such as sucrose soyate, sucrose behenate and sucrose stearate as products of reactions with fatty acid feedstocks derived from natural sources, the term is It is meant to encompass all the various components typically found as a consequence of the source from which the fatty acid ester is produced.

  For use in the methods and compositions of the present development, suitable sucrose esters are obtained by transesterification of sucrose with fatty acid glycerides obtained from soybean oil, or from behenic acid or stearic acid and mixtures thereof from natural sources. Synthesized by transesterification with derivatized ester or glyceride. Such sucrose esters are referred to herein as sucrose “soyate”, sucrose “behenate” and sucrose “stearate”, respectively.

  For use in the compositions of the present invention, sucrose esters esterified with stearates or hydrogenated soyate moieties such as sucrose stearate are particularly suitable. Commercially available stearic acid is a mixture of saturated and unsaturated linear fatty acid species having 12 to 18 carbon atoms in the aliphatic portion of the acid referred to herein as the “stearyl” group. It will be understood that there is.

  It will further be appreciated that other saccharides and polyfunctional alcohols can be esterified to provide ester lubricants that provide the volume density of the fatty acid moieties provided by the sucrose esters described above. Examples of these esters are the polyesters described in US Pat. No. 6,504,003 by Trout et al. And 6,121,440 by Kenneally et al., Incorporated herein by reference. Replacing some or all of the sucrose ester in the above composition with a polyester lubricant as described above is similarly improved over an extrudable PVC composition that does not include either the polyester or polysaccharide ester described above. It is believed that a composition with improved dynamic processing improvements will be provided.

  The amount of polysaccharide ester in the composition of the invention will vary widely depending on a number of factors including the desired level of improvement in processing parameters and / or the desired specific properties of the extrudable PVC composition. There can be. In a preferred embodiment, the composition comprises from about 0.01 to about 2 parts by weight of a polysaccharide ester per 100 parts by weight of the resin in the composition (hereinafter "per 100 parts by weight of resin" is abbreviated as PHR). Preferably, sucrose ester is included. In other embodiments, the composition has a polysaccharide ester of about 0.05 PHR to about 0.9 PHR, preferably a sucrose ester, more preferably about 0.1 PHR to about 0.8 PHR, and even more preferably about 0.00. It preferably contains from 1 PHR to about 0.4 PHR.

Resin The composition of the present invention may include one or more thermoplastic resins that are thermoplastic or otherwise extrudable. Therefore, it is considered that resins such as polycarbonate, ABS plastic and high engineering plastic can be used. In general, however, the resins of the present composition include vinyl base resins, ie, one or more polymers that share a vinyl group (CH ₂ ═CH) as a starting structural unit (homopolymers, copolymers, terpolymers, etc.). And preferably consists essentially of it. Particularly preferred are polyvinyl chloride (PVC), specifically suspension, dispersion, emulsion or bulk PVC resin, with suspension and bulk PVC resin being preferred. In a preferred embodiment, the PVC resin of the present invention has a Filentscher K value of from about 50 to about 70, even more preferably from about 55 to about 65.

Additives As noted above, the extrudable compositions of the present invention include extrudable compositions as described above, including those having thermal stability and those having internal and external lubricity. Preferably, other additives typically included in the PVC resin may be included. In the present specification, these are referred to as “supplemental” in distinction from the polysaccharide esters of the present invention which also have lubricity and thermal stability. Thus, the amount of polysaccharide ester used can be adjusted by the amount of supplemental lubricants, stabilizers, etc. in the composition according to known principles.

  The extrudable compositions of the present invention can be made by any known means of blending solid or semi-solid materials with other solid, semi-solid or liquid materials. Any type of mixing or blending device on a scale from a manual laboratory bench scale, eg, a motorized mixer and container with handles to a motorized industrial scale processing device can be used. Examples of the latter type of equipment include Henschel mixers and ribbon blenders.

  Conveniently, the extrudable composition is placed in a blending device with a weighed amount of resin, preferably a polyvinyl chloride resin (PVC resin), and in turn, the desired supplemental additive components, such as , Stabilizers, fillers, processing aids, colorants and pigments, and other ingredients desired in the composition, and further to 100 parts by weight of PVC resin added to the composition to the material as described above. It can be prepared by adding one or more sucrose esters in an amount corresponding to about 0.01 to about 2 parts by weight. Thus, for 100 parts by weight of PVC resin (PHR) contained in the composition, the composition further comprises from about 0.01 to about 2 parts by weight of the material comprising one or more sucrose esters. I will.

Additive Composition The present invention also provides an additive composition. In one embodiment, the additive composition of the present invention is added to a composition comprising an extrudable resin, preferably a PVC resin, optionally together with other additives, as defined herein. So as to provide an extrudable composition having improved processing and / or extrudate properties.

  In general, the additive composition can include any of the additives described above for use in the extrudable composition. Additional internal and external lubricants, heat stabilizers, and other components of the extrudable PVC composition, and the variables that govern the selection and amount of these supplemental additives used in the extrudable PVC composition are: Generally, it is described in Plastics Additives and Modifiers Handbook, Ed. J. Edenbaum, Van Nostrand Reinhold, New York 1992, which is partially incorporated herein. Suitable additive compositions include at least one polysaccharide ester and at least one member of the group consisting of a compatible supplemental lubricant and a compatible supplemental heat stabilizer.

  For example, in one embodiment, the additive composition of the present invention can be formulated to include all the components that make up the extrudable PVC composition, excluding the PVC resin. This type of additive composition is formulated to provide an extrudable PVC composition by being mixed with the PVC resin alone. In another embodiment, the additive composition is formulated to be added to the extrudable PVC composition as one of a number of additive components used to make the extrudable composition. Can do. In the latter embodiment, it is preferred that the additive composition comprises at least some of the most common components of the extrudable PVC composition, thereby being used in a number of different extrudable PVC compositions. It provides a single additive composition that can be simultaneously reduced while reducing the number of addition steps required to produce an extrudable PVC composition.

  It is believed that a wide range of ingredients over a wide range of relative proportions may be suitable for use in the present invention given the content contained herein. Furthermore, the content contained herein will enable one of ordinary skill in the art to readily determine whether a particular extrudable composition additive is compatible with a particular polysaccharide ester. It's thought to be.

  The additive composition of the present invention is a miscible material, such as a technique used to mix a mixture of two or more components to form a single phase, and two or more immiscible or partially immiscible. Solid, semi-solid or liquid materials can be mixed with other solid, semi-solids, including techniques used to blend phase-separated materials to form a homogeneous interpenetrating structure in the domain separation region of a miscible material Or it can be produced by any known means for mixing with liquid materials. Any type of mixing or blending device on a scale from a manual laboratory bench scale, eg, a motorized mixer and container with a handle to a motorized industrial scale processing device can be used. Examples of the latter type of equipment include a Henschel mixer and a temperature controlled stirred blend tank. It will be understood that the additive composition of the present invention can be prepared as a separate component for mixing with the types of extrudable compositions described above. Alternatively, the components of the additive composition can each be added separately, simultaneously or sequentially, to the extrudable PVC composition without first blending them together. Furthermore, it will be understood that when added to an extrudable PVC composition as a series of components, generally the order of addition is not critical.

  Examples of supplemental internal lubricants suitable for use in the manufacture of lubricant-based additive compositions include metal soaps such as calcium stearate and fatty acid ester waxes known to be internal lubricants For example, distearyl phthalate is included. Examples of supplemental external lubricants suitable for use in the manufacture of lubricant-based additive compositions include hydrocarbon waxes such as paraffin wax, amide waxes such as ethylene bis (stearamide) wax, polyethylene wax, For example, AC (registered trademark) 6A (Honeywell) and oxidized polyethylene wax, such as AC (registered trademark) 629A (Honeywell). In a preferred embodiment, the additive composition comprises a polysaccharide ester, preferably a sucrose ester, and a supplemental lubricant selected from the group consisting of paraffin wax lubricant, oxidized polyethylene lubricant and combinations thereof. For additive compositions containing paraffin lubricants, in some embodiments, it is preferred that calcium hydroxide and fatty acids are further included in the composition. Alternatively, the composition may instead include the direct addition of fatty acid salts.

  In general, an additive composition consisting essentially of sucrose ester and a wax lubricant, such as Rheolub® 165 Paraffin Wax (Honeywell). The compositions preferably comprise from about 1% to about 50% polysaccharide ester, more preferably from about 5% to about 30% polysaccharide ester, and even more preferably from about 5% to about 25%. Contains sucrose esters, and is generally suitable for use. The compositions are preferably from about 1% to about 99% by weight wax lubricant, more preferably from about 20% to about 85% by weight wax lubricant, and even more preferably from about 30% to about 80% by weight. In general, paraffin wax lubricants are suitable for use.

  In general, an additive composition consisting essentially of a polysaccharide ester (preferably sucrose ester) and an oxidized polyethylene lubricant, such as A-C629® (Honeywell), is preferably about 1 wt% to about 99 wt%. % Polysaccharide ester, more preferably from about 9% to about 56% by weight polysaccharide ester, and from about 1% to about 75% by weight oxidized polyethylene lubricant, even more preferably from about 7% to about 45% by weight. % Polyethylene lubricant.

  In general, when the additive composition comprises a blend of one or more paraffin wax lubricants and one or more oxidized polyethylene lubricants, the composition is preferably (a) from about 5% to about 85 wt% sucrose ester, more preferably from about 5 wt% to about 30 wt%, more preferably from about 7 wt% to about 20 wt% sucrose ester; (b) from about 10 wt% to about 90 wt% Paraffin wax lubricant, more preferably from about 30% to about 70% by weight paraffin wax lubricant; and (c) from about 5% to about 20% by weight oxidized polyethylene lubricant, more preferably from about 7% by weight. Contains about 15% by weight oxidized polyethylene lubricant.

  If a paraffin wax lubricant is present with or without further lubricant, the additive composition optionally includes calcium hydroxide and a fatty acid such as stearic acid. In general, the weight ratio of calcium hydroxide: fatty acid is preferably from about 1: 4 to about 1:10, more preferably from about 1: 7 to about 1:10, and even more preferably about 1: 9. . Preferably, the amount of calcium hydroxide and fatty acid combination in the composition is up to about 1.1 times the amount by weight of the remaining components of the additive composition, even more preferably The amount is from about 0.02 to about 1 times the weight of the combination of ingredients.

  In general, if the composition contains fatty acid and calcium hydroxide components, the composition is preferably extrudable after the liquid wax and fatty acid are blended together and the finished additive composition is to be blended Produced by carrying out the reaction step under conditions in which at least a portion of the fatty acids are neutralized, as defined by variables that are technically certified with respect to the desired properties of the PVC composition. Preferably, the mixing and temperature conditions at which the ingredients of the additive composition, including fatty acids and calcium hydroxide, can be reached during blending until the neutralization reaction between the hydroxide and the acid is substantially complete. Adjusted to make sure progress. After this, any additional internal or external lubricant to be included in the composition is preferably melt blended sequentially into the material and any other additives or processing aids to be included. Add The material is then preferably processed by known means such as filtering and making it suitable for use as an additive, such as prilling, flaking, pasting and slabning.

  As noted above, instead of adding calcium hydroxide and fatty acid to the additive composition, a fatty acid salt, such as calcium stearate, is typically added to the composition, typically the weight of the combination of other ingredients in the composition. It can be added in an amount up to about 1.1 times on a weight basis. Larger amounts of fatty acid salts can be added depending on the known variables. In general, when the additive composition includes a fatty acid salt, the components are preferably dry blended according to the principles described herein.

  As described above, an additive composition consisting essentially of at least one sucrose ester and at least one component constituting a supplemental heat stabilizing additive can be produced. Supplementary thermal stabilizers that have physical properties similar to paraffin wax lubricants and can act like a “carrier” to which sucrose esters can be blended for use when formulating such additive compositions Is preferably used. It is understood that the same process described above for the manufacture of a lubricant-based additive composition can be used in the manufacture of a heat stabilizer-based additive composition. Will.

  As used herein, the term “supplemental heat stabilizer” refers to any supplemental additive that is known to have a dynamic thermal stabilization effect when added to an extrudable PVC composition. Is also included. Examples of supplemental heat stabilizers suitable for use in the manufacture of additive compositions include those commonly used as heat stabilizing additives in extrudable PVC compositions, such as compounds containing tin For example, tin mercaptide is included. Other technically approved heat stabilizers, such as those generally described in Plastics Additives and Modifiers Handbook, Ed. J. Edenbaum, Van Nostrand Reinhold, New York 1992 (incorporated herein) For example, you may use what uses a lead base compound as a base material, for example, neutral lead stearate and dibasic lead phosphate. In addition, “mixed metal” soaps such as calcium stearate / zinc may be used. In addition, heat stabilizers that are not based on heavy metal salts, such as organic substrate stabilizers (OBS) manufactured by Crompton Corporation may be used. As in the case of the above technically certified lubricant-based additive composition, the technically certified heat stabilizer-based additive composition is further included in the extrudable PVC composition. It will be understood that any other additive component typically incorporated in may be included.

The following examples are presented for the purpose of further illustrating the foregoing description and are not intended to limit the scope of the claimed invention.
EXAMPLE A PVC resin-containing extrudable composition of the present invention (Example 1) and the same ingredients but with a known external lubricant (Comparative Example A) and a known internal lubricant (Comparative Example B) sucrose ester lubricant Two similar compositions substituting are shown below.

  The compositions were prepared by placing the components in a Warning Blender (high intensity mixer) and heating to temperatures above 105 ° C. while operating the mixing blade. When the ingredients were uniformly blended, the composition was drained, cooled to ambient temperature and allowed to stand for 24 hours (aging period).

  At the end of the aging period, a 68 g sample from the composition was placed in a Brabender torque rheometer for rheometric analysis. As described above, each composition was subjected to rheometric analysis of melting and stabilization times, equilibrium and melting torques, and equilibrium temperatures according to ASTM standard test method D2538-02. Using this procedure, a comparison of defined rheometric properties can be made by comparing the composition of the present invention (Example 1) and two comparative compositions, namely Comparative Example A (external lubricant instead of sucrose ester lubricant). ) And Comparative Example B (containing internal lubricant instead of sucrose ester lubricant). The results of these measurements are shown in Table II and discussed below.

The materials used to make the compositions of the various examples and comparative examples were as follows. 1091 (registered trademark) polyvinyl chloride resin (resin) manufactured by Georgia Gulf; TM281 (registered trademark) tin-based heat stabilizer (thermal stabilizer) manufactured by Rohm &Haas; Rheolub® 165 paraffin wax manufactured by Honeywell (Paraffin wax), COAD 10 (R) calcium stearate (calcium lubricant) from Norac; AC (R) 629 oxidized polyethylene wax (polymer wax) from Honeywell; K120N (R) acrylic from Rohm & Haas KM334 (registered trademark) acrylic impact modifier (impact modifier) manufactured by Rohm &Haas; UFT (registered trademark) calcium carbonate (calcium carbonate) manufactured by OMYA; titanium dioxide (TiO ₂ ), stearyl stearate (ester lubricant “a”) and distearyl phthalate (ester lubricant “a” b ") is a commercial product; and sucrose stearate (ester lubricant" c ") was obtained from Procter & Gamble. All materials were used as received.

  Two comparative examples and one example composition were prepared as described above using the materials listed in Table I below in the indicated amounts.

  The composition thus produced was subjected to rheological analysis as described above. When performing the analysis, the rheometer bowl temperature was set to 180 ° C. and the rotor speed was set to 80 rpm. The results of this analysis are shown in Table II below.

  These data show that PVC resin-containing compositions including sucrose ester lubricants have superior extrusion properties than compositions containing only technically approved lubricants (Comparative Examples A and B). . The decrease in equilibrium temperature and torque due to the sucrose ester compared to the internal lubricant suggests that the sucrose ester lubricant works in part in the internal lubricant mode. It further shows that sucrose esters provide an apparent viscosity reduction that is superior to that provided by known distearyl phthalate internal lubricants.

  These data further show that the compositions of the present invention show a decrease in melt torque without an associated increase in melt time when compared to stearyl stearate external lubricants. This suggests that the sucrose ester acts in part as an external lubricant with properties superior to stearyl stearate.

  Table II further surpasses prior art compositions in which the processing properties of the compositions (containing sucrose esters) of the present invention contain only supplemental lubricants that are tailored to give similar levels of lubricity. It shows improved and dynamic thermal stability exceeds that of the prior art compositions. From these data, the composition of the present invention requires less extruder torque and / or less extruder head pressure for the same extrusion rate of the PVC composition when compared to the comparative composition. It's thought to be. Furthermore, the compositions of the present invention provide extrudates with superior surface gloss due to the superior external lubricant performance afforded by the sucrose ester composition over compositions containing only technically recognized external lubricants. It is thought that. As noted above, the data in Table II also shows that the composition exhibits increased dynamic thermal stability, as indicated by increased thermal stabilization time.

Examples II-VI-Additive Composition The following are the seven types of (i) sucrose ester and paraffin wax lubricant (Example II); (ii) sucrose ester and oxidized polyethylene lubricant (Example III); (iii) Sucrose ester, paraffin wax lubricant and oxidized polyethylene lubricant (Example IV); (iv) Sucrose ester, paraffin wax lubricant, calcium hydroxide and stearic acid (Example V); (v) Sucrose ester, oxidized polyethylene lubricant, paraffin wax (Vi) sucrose ester, paraffin wax lubricant and calcium stearate (Example VII); and (vii) sucrose ester, oxidized polyethylene lubricant, paraffin wax lubricant and calcium stearate (Example VI); Addition including Example VIII) Is a composition examples. In all of the example preparations, the sucrose stearate listed is a product obtained from Procter & Gamble, the listed paraffin wax is RL-165-010 (registered trademark) (Honeywell), The oxidized polyethylene wax listed is AC®-629 (Honeywell), the calcium hydroxide listed is a commercial product, and the stearic acid listed is a commercial brand from Procter & Gamble. Material.

  In the following examples, melt blending means that the paraffin and polyethylene components of the composition are placed in a blend tank and heated to about 132 ° C. The ingredients are blended for about 1 hour, and the time is adjusted as needed to provide a uniform mixture of the materials. When the paraffin component and the polyethylene component are uniform, sucrose stearate is first added, and then any remaining components are added to the material sequentially. If the composition requires the production of an acid salt by blending base and fatty acid into the composition, the blending is continued until the desired acid number is reached. As each ingredient is added to the container, blending is carried out for about 15 minutes between additions and for an additional hour after the addition of the last ingredient. The blended material is then filtered through a bag filter and prilled.

  As shown in some examples, a dry blend method is used. The dry blending process involves placing the sucrose ester and other components of the composition in a ribbon blender under ambient conditions and blending the components for a time sufficient to provide a homogeneous mixture of the components. Typically this is achieved after a blend time of about 30 minutes.

  As described in each example, the improved extrusion properties expected by adding a specified amount of composition to an extrudable PVC composition include the PVC composition with which the additive composition is blended together. Reducing the head pressure and / or extrusion torque required to extrude and / or increasing the dynamic thermal stability of the PVC composition and / or increasing the required surface gloss of the extrudate containing the blend.

Example II
The additive composition is made by melt blending 9 g sucrose stearate and 33.1 g paraffin wax at a temperature of about 132 ° C. according to the procedure described above. When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudability properties of the extrudable PVC composition are improved. Is considered to be accepted.

Example III
The additive composition is made by melt blending 9 g sucrose stearate and 7.2 g oxidized polyethylene wax at a temperature of about 132 ° C. according to the procedure described above. When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudability properties of the extrudable PVC composition are improved. Is considered to be accepted.

Example IV
The additive composition is made by melt blending 9 g sucrose stearate, 33.1 g paraffin wax and 7.2 g oxidized polyethylene wax at a temperature of about 132 ° C. according to the procedure described above. When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudability properties of the extrudable PVC composition are improved. Is considered to be accepted.

Example V
The additive composition is prepared by melt blending 9 g sucrose stearate and 33.1 g paraffin wax (Honeywell) at a temperature of about 132 ° C. according to the procedure described above. After blending the wax and sucrose stearate for about 15 minutes, about 5.1 g calcium hydroxide and 45.6 g stearic acid are added to the mixture. The mixture is heated to about 155 ° C. and held at a temperature of at least 150 ° C. with continuous blending until the mixture is titrated to produce an acid number of 22-24 g KOH / g mixture.

  When blended with the PVC composition in an amount sufficient to provide about 0.1 part by weight of the PVC resin contained in the aliquot of the extrudable PVC composition with the PVC composition, the extrudable PVC It is believed that improvements in the extrusion properties of the composition will be observed.

Example VI
The additive composition is obtained by adding 5.1 g of calcium hydroxide and 45.6 g of stearic acid to the 49.3 g additive composition prepared according to Example IV according to the procedure described for Example V. Manufactured by.

  When blended with the PVC composition in an amount sufficient to provide about 0.1 part by weight of the PVC resin contained in the aliquot of the extrudable PVC composition with the PVC composition, the extrudable PVC It is believed that improvements in the extrusion properties of the composition will be observed.

Example VII
The additive composition is prepared by dry blending 9 g sucrose stearate and 33.1 g paraffin wax under ambient conditions in a ribbon blender under ambient conditions according to the dry blend method described above. After the initial blending time, 50 g of calcium stearate is added to the mixture and then blended for about an additional hour.

  When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudability properties of the extrudable PVC composition are improved. Is considered to be accepted.

Example VIII
The additive composition is made by dry blending 9 g sucrose stearate, 33.1 g paraffin wax and 7.2 g oxidized polyethylene wax in a ribbon blender under ambient conditions according to the procedure described above. After the initial blending time, 50 g of calcium stearate is added to the mixture and then blended for about an additional hour.

  When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudable PVC composition improves the extruding properties Is considered to be accepted.

The following describes an additive composition comprising a technically certified heat stabilizer and sucrose stearate.
Example IX
The additive composition was prepared by dry blending 9 g sucrose stearate and 5 g Mark A70® (OBS heat stabilizer, Crompton Corporation, used as received) under ambient conditions according to the dry blend method described above. To make. Blending is performed until a uniform mixture is obtained.

When blended with an aliquot of the PVC resin-containing extrudable PVC composition in an amount sufficient to provide about 0.1 parts by weight of the sucrose ester PHR, the extrudability properties of the extrudable PVC composition are improved. Is considered to be accepted.

Claims (24)

A method of extruding a resin-containing composition comprising:
(A) providing an extrudable material comprising at least one extrudable resin and at least one polysaccharide ester of formula I :

Wherein A is independently hydrogen or the structure I:

Wherein R is independently an aliphatic or aromatic moiety having 8 to 40 carbon atoms, and at least 50% by weight of the A moiety of the compound of formula I is all Including a portion of structure I] ; and (b) extruding the extrudable material to produce an extrudate;
Including methods.   The method of claim 1, wherein the polysaccharide ester is present in an amount effective to increase the dimensional stability of the extrudate relative to the use of the same composition without the polysaccharide ester. The extrusion process produces an extruder head pressure, wherein the polysaccharide ester is present in an amount effective to reduce the extruder head pressure relative to the use of the same composition without the polysaccharide ester; The method of claim 1. The resulting extrusion process the extruder torque, in which the polysaccharide ester is present in an amount effective to reduce the required extruder torque as compared to the use of the polysaccharide ester not the same composition containing, The method of claim 1. The polysaccharide ester is present in an amount effective to improve the extrudability of the extrudable material as compared to the extrudability of the extrudable material in the absence of the polysaccharide ester, A method according to claim 1 .   The method of claim 1, wherein the polysaccharide ester is present in an amount effective to increase extrudate gloss relative to the use of the same composition without the polysaccharide ester. The polysaccharide ester increases (a) the extrudability of the extrudable material, the gloss of the extrudate or the dimensional stability of the extrudate by at least 10% compared to the use of the same composition without the polysaccharide ester. Or (b) present in an amount effective to reduce the head pressure or extruder torque of the extruder by at least 10% compared to the use of the same composition without the polysaccharide ester. 7. The method according to any one of 6. The polysaccharide ester (a) increases the extrudability of the extrudable material or the dimensional stability of the extrudate by at least 10% compared to the use of the same composition without the polysaccharide ester; or (b) An extruder head pressure or extruder torque is present in an amount effective to reduce by at least 10% compared to the use of the same composition without the polysaccharide ester, wherein the extrudate gloss is 6. A method according to any of claims 2 to 5, wherein there is substantially no reduction compared to the use of the same composition without ester. The polysaccharide ester reduces (a) the head pressure or extruder torque of the extruder by at least 10% compared to the use of the same composition without the polysaccharide ester; or (b) of the extrudable material Present in an amount effective to increase extrudability or gloss of the extrudable material by at least 10% compared to the use of the same composition without the polysaccharide ester, wherein the dimensional stability of the extrudate 7. A method according to any of claims 3 to 6, wherein is not substantially reduced compared to the use of the same composition without said polysaccharide ester.   The method of claim 1, wherein the polysaccharide ester is present in an amount effective to increase the dynamic thermal stability of the extrudable material relative to the material in the absence of the polysaccharide ester. The method of claim 1, wherein the resin is polyvinyl chloride. 2. The method of claim 1, wherein at least 70% by weight of the A moiety of the polysaccharide ester compound of formula I all comprises a moiety having structure I. 2. The method of claim 1, wherein the R moiety of structure I is a stearyl moiety. The method of claim 1 , wherein the amount of polysaccharide ester present in the extrudable composition is 0.01 PHR to 2 PHR . The method of claim 1, wherein the polysaccharide ester comprises sucrose soyate. The method of claim 1, wherein the polysaccharide ester comprises sucrose behenate. At least 70% by weight of said polysaccharide ester compound is octasubstituted with an A group of structure I, wherein the R group of structure I is linear or branched saturated or containing 8 to 40 carbon atoms The method of claim 1, comprising an aliphatic moiety that is unsaturated, which may be substituted with one or more halogen functional groups. The method of claim 1, wherein the R group comprises 12 to 25 carbon atoms. The method of claim 1 , wherein the amount of polysaccharide ester present in the extrudable composition is from 0.05 PHR to 0.9 PHR . The method of claim 1, wherein the extrudable material further comprises at least one lubricant selected from the group consisting of paraffin wax lubricant and oxidized polyethylene lubricant. The extrudable material further comprises a tin base heat stabilizers, organic base heat stabilizers, at least one selected from the group consisting of lead base heat stabilizers and mixed metal substrate heat stabilizers, claim 20. The method according to 20. The method of claim 21, further comprising a mixture of calcium hydroxide and stearic acid present in a ratio of 1: 6 to 1:10 . 24. The method of claim 22, wherein the extrudable composition further comprises calcium stearate. A method of forming an extrudable composition, comprising an extrudable resin and at least one additional component selected from the group consisting of at least one polysaccharide ester and a supplemental lubricant and a supplemental heat stabilizer Mixing an additive composition comprising :
Said at least one polysaccharide ester has the formula I:

Wherein A is independently hydrogen or the structure I:

Wherein R is independently an aliphatic or aromatic moiety having 8 to 40 carbon atoms, and at least 50% by weight of the A moiety of the compound of formula I is all , Including a portion of structure I] .