阅读说明：本技术 添加剂组合物和使用其制备聚合物组合物的方法 (Additive composition and method of preparing polymer composition using the same ) 是由 D·L·多森 徐晓友 W·福里斯特尔 C-C·蔡 于 2019-07-22 设计创作，主要内容包括：本发明涉及一种添加剂组合物,其包含一种或多种顺式-1,2-环己烷二甲酸钙盐。存在于添加剂组合物中的25摩尔％或更多的顺式-1,2-环己烷二甲酸钙盐是顺式-1,2-环己烷二甲酸钙一水合物。添加剂组合物的以重量分析的水含量为约20％或更少。制备热塑性聚合物组合物的方法需要将添加剂组合物与热塑性聚合物混合,使所得混合物熔融,并使混合物固化以制备聚合物组合物。(The present invention relates to an additive composition comprising one or more cis-1, 2-cyclohexanedicarboxylic acid calcium salts. 25 mole percent or more of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition is calcium cis-1,2-cyclohexanedicarboxylate monohydrate. The additive composition has a water content of about 20% by weight or less. The process for preparing the thermoplastic polymer composition requires mixing the additive composition with the thermoplastic polymer, melting the resulting mixture, and allowing the mixture to solidify to prepare the polymer composition.)

1. An additive composition comprising one or more cis-1, 2-cyclohexanedicarboxylic acid calcium salts, wherein 25 mole% or more of the cis-1, 2-cyclohexanedicarboxylic acid calcium salts present in the additive composition are cis-1, 2-cyclohexanedicarboxylic acid calcium monohydrate, and the additive composition has a water content by weight of about 20% or less.

2. The additive composition of claim 1, wherein the additive has a water content of 2% to about 20% by weight.

3. The additive composition of claim 1 or 2, wherein about 33 mole% or more of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition is calcium cis-1,2-cyclohexanedicarboxylate monohydrate.

4. The additive composition of claim 3, wherein about 50 mole% or more of the cis-1,2-cyclohexanedicarboxylate calcium salt present in the additive composition is cis-1,2-cyclohexanedicarboxylate calcium monohydrate.

5. The additive composition of claim 4, wherein about 75 mole% or more of the cis-1,2-cyclohexanedicarboxylate calcium salt present in the additive composition is cis-1,2-cyclohexanedicarboxylate calcium monohydrate.

6. The additive composition of claim 5, wherein about 90 mole% or more of the cis-1,2-cyclohexanedicarboxylate calcium salt present in the additive composition is cis-1,2-cyclohexanedicarboxylate calcium monohydrate.

7. The additive composition of any one of claims 1-6, wherein the additive composition further comprises a fatty acid metal salt.

8. The additive composition of claim 7, wherein the fatty acid is selected from C₈-C₂₈A fatty acid.

9. The additive composition of claim 8, wherein the fatty acid is selected from C₁₂-C₂₂A fatty acid.

10. The additive composition of claim 9, wherein the fatty acid is stearic acid.

11. The additive composition of any of claims 7-10, wherein the fatty acid metal salt comprises a cation selected from the group consisting of: alkali metal cations, alkaline earth metal cations, and cations of group 12 elements.

12. The additive composition of claim 11, wherein the fatty acid metal salt comprises a cation of a group 12 element.

13. The additive composition of claim 12, wherein the fatty acid metal salt comprises zinc cations.

14. The additive composition of claim 13, wherein the additive composition further comprises zinc stearate.

15. A method of making a polymer composition, the method comprising the steps of:

(a) providing a thermoplastic polymer, said thermoplastic polymer having a melting point;

(b) providing an additive composition according to any one of claims 1-14;

(c) combining the thermoplastic polymer and the additive composition to produce a mixture;

(d) heating the mixture to a temperature above the melting point of the thermoplastic polymer to produce a molten mixture; and

(e) reducing the temperature of the molten mixture to a temperature below the melting point of the thermoplastic polymer, thereby producing a polymer composition.

16. The method of claim 15, wherein the thermoplastic polymer is a polyolefin.

17. The method of claim 16, wherein the polyolefin is polypropylene.

18. The method of claim 16, wherein the polyolefin is polyethylene.

19. The method of any one of claims 15-18, wherein the mixture comprises from about 50ppm to about 5,000ppm of the calcium salt of cis-1, 2-cyclohexanedicarboxylate.

20. The method of claim 19, wherein the mixture comprises from about 100ppm to about 2,000ppm of the cis-1,2-cyclohexanedicarboxylate calcium salt.

Technical Field

The present application relates to additive compositions suitable for use as crystallization nucleators for polymers, methods of preparing polymer compositions using such additive compositions, and polymer compositions prepared using such methods.

Background

Several nucleating agents for thermoplastic polymers are known in the art. Typically, these nucleating agents act by forming nuclei or providing sites for the formation and/or growth of crystals in the thermoplastic polymer as it solidifies from a molten state. The nuclei or sites provided by the nucleating agent allow crystals to form within the cooled polymer at a higher temperature and/or at a faster rate than crystals form within the original non-nucleated thermoplastic polymer. These effects may then allow the nucleated thermoplastic polymer composition to be processed with a shorter cycle time than the original non-nucleated thermoplastic polymer.

Although polymeric nucleating agents may function in a similar manner, the function of not all nucleating agents is the same. For example, certain nucleating agents may be very effective in increasing the peak polymer recrystallization temperature of a thermoplastic polymer, but the rapid crystallization rate caused by such nucleating agents may result in inconsistent (anisotropic) shrinkage of molded parts produced from thermoplastic polymer compositions containing the nucleating agents. Such nucleating agents may also be ineffective in increasing the stiffness of the molded article to the desired degree.

In view of the complex interrelationship of these properties and the fact that many nucleating agents exhibit less than optimal performance in at least one aspect, there remains a need for nucleating agents that are capable of producing thermoplastic polymer compositions that exhibit a more desirable combination of high peak polymer recrystallization temperature, low and isotropic shrinkage, and high stiffness. The additive compositions, polymer compositions, and methods of their preparation described herein seek to meet this need.

Disclosure of Invention

In a first embodiment, the present invention provides an additive composition comprising one or more calcium cis-1,2-cyclohexanedicarboxylate salts, wherein 25 mole% or more of the calcium cis-1,2-cyclohexanedicarboxylate salts present in the additive composition are calcium cis-1,2-cyclohexanedicarboxylate monohydrate. The additive composition preferably has a gravimetric water content (gravimetric water content) of about 20% or less.

In a second embodiment, the present invention provides a method of making a polymer composition, the method comprising the steps of: (a) providing a thermoplastic polymer, said thermoplastic polymer having a melting point; (b) providing an additive composition as described above; (c) combining the thermoplastic polymer and the additive composition to produce a mixture; (d) heating the mixture to a temperature above the melting point of the thermoplastic polymer to produce a molten mixture (molten addition); and (e) reducing the temperature of the molten mixture to a temperature below the melting point of the thermoplastic polymer, thereby producing a polymer composition.

Detailed Description

In a first embodiment, the present invention provides an additive composition comprising one or more cis-1, 2-cyclohexanedicarboxylic acid calcium salts. Preferably, the additive composition comprises calcium cis-1,2-cyclohexanedicarboxylate monohydrate (i.e., CaC)₈H₁₀O₄·1H₂O) and one or more other salts of cis-1, 2-cyclohexanedicarboxylic acid calcium such as anhydrous calcium cis-1,2-cyclohexanedicarboxylate (i.e., CaC)₈H₁₀O₄)。

The calcium cis-1,2-cyclohexanedicarboxylate monohydrate can be present in the additive composition in any suitable amount. In one embodiment, the amount of calcium cis-1,2-cyclohexanedicarboxylate monohydrate may be expressed as a percentage of the total amount of the calcium cis-1,2-cyclohexanedicarboxylate salt present in the additive composition. In such embodiments, 25 mole% or more of the cis-1,2-cyclohexanedicarboxylate calcium salt present in the additive composition is cis-1,2-cyclohexanedicarboxylate calcium monohydrate. More preferably, about 33 mole% or more, about 50 mole% or more, about 75 mole% or more, about 90 mole% or more, or about 95 mole% or more of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition is calcium cis-1,2-cyclohexanedicarboxylate monohydrate.

Although the additive composition comprises hydrated cis-1, 2-cyclohexanedicarboxylic acid calcium salt, the additive composition preferably comprises a limited amount of water. Preferably, the additive composition has a water content of about 20% by weight or less. More preferably, the additive composition has a water content by weight of about 15% or less, or about 10% or less. Since the additive composition contains some calcium cis-1,2-cyclohexanedicarboxylate monohydrate, the gravimetric water content of the additive composition will be greater than zero. Thus, in a preferred embodiment, the additive composition has a water content by weight of about 2% or greater. In other preferred embodiments, the additive composition has a water content by weight of about 3% or more, about 4% or more, about 5% or more, about 6% or more, or about 7% or more. Thus, in a series of preferred embodiments, the water content of the additive composition, as measured by weight, is preferably from 2% to about 20% (e.g., from about 2% to about 15%, or from about 2% to about 10%), from about 3% to about 20% (e.g., from about 3% to about 15%, or from about 3% to about 10%), from about 4% to about 20% (e.g., from about 4% to about 15%, or from about 4% to about 10%), from about 5% to about 20% (e.g., from about 5% to about 15%, or from about 5% to about 10%), from about 6% to about 20% (e.g., from about 6% to about 15%, or from about 6% to about 10%), or from about 7% to about 20% (e.g., from about 7% to about 15%, or from about 7% to about 10%).

In addition to the above-described cis-1, 2-cyclohexanedicarboxylic acid calcium salt, the additive composition may also comprise other components. Suitable additional components include, but are not limited to, antioxidants (e.g., phenolic antioxidants, phosphite antioxidants, and combinations thereof), antiblock agents (e.g., amorphous silica and diatomaceous earth), pigments (e.g., organic and inorganic pigments) and other colorants (e.g., dyes and polymeric colorants), fillers and reinforcing agents (e.g., glass fibers, talc, calcium carbonate)And magnesium oxysulfate whiskers), nucleating agents, clarifying agents, acid scavengers (e.g., hydrotalcite-like acid scavengers [ e.g., from Kisuma Chemicals)Fatty acid metal salt [ e.g. stearic acid metal salt]And metal salts of fatty acid esters [ e.g. lactates]Polymer processing additives (e.g., fluoropolymer processing aids), polymeric crosslinkers, slip agents (e.g., fatty acid amide compounds derived from the reaction between fatty acids and ammonia or amine-containing compounds), fatty acid ester compounds (e.g., fatty acid ester compounds derived from the reaction between fatty acids and hydroxyl-containing compounds such as glycerol, diglycerol, and combinations thereof), and combinations thereof.

In a preferred embodiment, the additive composition further comprises a fatty acid metal salt. Suitable fatty acid metal salts include, but are not limited to, saturated and unsaturated (i.e., monounsaturated and polyunsaturated) fatty acids (e.g., C)₆Or higher fatty acids) and esters of such saturated and unsaturated fatty acids (e.g., lactic acid or poly (lactic acid) esters). In a preferred embodiment, the fatty acid is selected from saturated and unsaturated C₈-C₂₈Fatty acids, more preferably saturated and unsaturated C₁₂-C₂₂A fatty acid. More preferably, the fatty acid is selected from saturated C₈-C₂₈Fatty acids, even more preferably saturated C₁₂-C₂₂A fatty acid. In a more specific preferred embodiment, the additive composition comprises at least one fatty acid metal salt selected from the group consisting of: laurate, myristate, palmitate, stearate (e.g., stearate and 12-hydroxystearate), arachinate (eicosanoate), behenate, lactate (lactylate), and mixtures thereof. In a preferred embodiment, the additive composition comprises at least one fatty acid metal salt selected from the group consisting of myristate, palmitate, stearate and mixtures thereof. In a further preferred embodiment, the additive composition comprises at least one fatty acid metal salt selected from the group consisting of myristate, stearate and mixtures thereof. More preferably, the additiveThe composition comprises a metal stearate. The fatty acid metal salts described above are typically derived from natural sources and therefore comprise a mixture of fatty acid salts having different carbon chain lengths. For example, products sold as stearates may contain significant amounts of palmitates and/or arachidates. Furthermore, the distribution of the different fatty acid salts in the product may vary depending on the particular source used to prepare the product. Thus, as used in this application, reference to a metal salt of a particular fatty acid salt is not intended to encompass only a pure fatty acid salt. Conversely, reference to a particular fatty acid salt also encompasses products that are commercially available as that particular fatty acid salt, even though such products also contain measurable amounts of fatty acid salts having similar carbon chain lengths.

The fatty acid salt may comprise any suitable counter ion to balance the charge of the fatty acid anion. As mentioned above, the counter ion is preferably a metal cation. In a preferred embodiment, the fatty acid metal salt comprises a cation selected from the group consisting of: alkali metal cations, alkaline earth metal cations, and cations of group 12 elements. More preferably, the fatty acid metal salt contains a cation selected from the group consisting of cations of group 12 elements. Most preferably, the fatty acid metal salt comprises zinc cations (i.e., zinc (II) cations).

The fatty acid salt can be present in the additive composition in any suitable amount. In a preferred embodiment, the fatty acid salt is present in the additive composition in an amount of: about 1 part by weight or more of the fatty acid salt per 19 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition. In a further preferred embodiment, the fatty acid salt is present in the additive composition in an amount of: about 1 part by weight or more of a fatty acid salt per 9 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 1 part by weight or more of a fatty acid salt per 4 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 1 part by weight or more of a fatty acid salt per 3 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 3 parts by weight or more of a fatty acid salt per 7 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; or about 1 part by weight or more of the fatty acid salt per 2 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition. Preferably, the fatty acid salt is present in the additive composition in an amount of: about 9 parts by weight or less of a fatty acid salt per 1 part by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 4 parts by weight or less of a fatty acid salt per 1 part by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 3 parts by weight or less of a fatty acid salt per 1 part by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 7 parts by weight or less of a fatty acid salt per 3 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 3 parts by weight or less of a fatty acid salt per 2 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; about 1 part by weight or less of a fatty acid salt per 1 part by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition; or about 2 parts by weight or less of the fatty acid salt per 3 parts by weight of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition. Thus, in a series of preferred embodiments, the fatty acid salt and the calcium salt of cis-1,2-cyclohexanedicarboxylate are present in the additive composition in a ratio of from about 1:19 to about 9:1, from about 1:9 to about 4:1, from about 1:4 to about 3:1, from about 3:7 to about 7:3, from about 1:2 to about 3:2, from about 1:2 to about 1:1, or from about 1:2 to about 2:3 (which ratio is expressed as the ratio of parts by weight of the fatty acid salt to parts by weight of the calcium salt of cis-1, 2-cyclohexanedicarboxylate). Preferably, the fatty acid salt is present in the additive composition in an amount of: about 1 part of fatty acid salt per 2 parts of the calcium salt of cis-1,2-cyclohexanedicarboxylate present in the additive composition.

As noted above, it is believed that the additive composition is particularly suitable for use as a nucleating agent for thermoplastic polymers, particularly polyolefins such as polypropylene. It has been observed that polymer compositions made with the above additive compositions exhibit a combination of desirable physical properties. For example, a polymer composition made with an additive composition according to the present invention (e.g., a polypropylene polymer composition) can exhibit a peak polymer recrystallization temperature in excess of 124 ℃, which is high enough to significantly shorten cycle times in some molding operations. These polymer compositions also exhibit relatively high stiffness relative to polymer compositions nucleated with additive compositions that do not contain significant amounts of calcium cis-1,2-cyclohexanedicarboxylate monohydrate. In addition, polymer compositions (e.g., polypropylene polymer compositions) made with the additive composition according to the present invention exhibit lower shrinkage in the machine and transverse directions as compared to similar polymer compositions nucleated with an additive composition that does not contain a significant amount of calcium cis-1,2-cyclohexanedicarboxylate monohydrate. Furthermore, the polymer compositions made with the additive composition according to the invention exhibit greater isotropic shrinkage, which means that parts made with the polymer composition have greater dimensional stability and are less likely to warp when exposed to varying temperatures. Lower shrinkage is generally considered a desirable feature because shrinkage of the polymer composition is directly related to the thermal expansion of the polymer composition upon heating. Thermal expansion of polymer compositions is of particular concern in applications where the polymer composition will be subjected to large temperature fluctuations, such as automotive trim applications (e.g., automotive bumpers). In such applications, the thermal expansion of the part must be tightly controlled to prevent the part from warping, deforming or impacting on adjacent metal pieces at high heat.

Accordingly, in a second embodiment, the present invention provides a method of making a polymer composition. The method comprises the following steps: (a) providing a thermoplastic polymer, said thermoplastic polymer having a melting point; (b) providing an additive composition according to the above; (c) combining the thermoplastic polymer and the additive composition to produce a mixture; (d) heating the mixture to a temperature above the melting point of the thermoplastic polymer to produce a molten mixture; and (e) reducing the temperature of the molten mixture to a temperature below the melting point of the thermoplastic polymer, thereby producing a polymer composition.

The process of the present invention may utilize any suitable thermoplastic polymer. Preferably, the thermoplastic polymer is a polyolefin. The polyolefin polymer may be any suitable polyolefin, such as polypropylene, polyethylene, polybutylene, poly (4-methyl-1-pentene), and poly (vinylcyclohexane). In a preferred embodiment, the thermoplastic polymer is a polyolefin selected from the group consisting of polypropylene homopolymers (e.g., atactic polypropylene homopolymers, isotactic polypropylene homopolymers, and syndiotactic polypropylene homopolymers), polypropylene copolymers (e.g., polypropylene random copolymers), polypropylene impact copolymers, and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, random copolymers made by polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene) and hex-1-ene (i.e., 1-hexene). In such polypropylene random copolymers, the comonomer can be present in any suitable amount, but is typically present in an amount less than about 10 weight percent (e.g., from about 1 to about 7 weight percent). Suitable polypropylene impact copolymers include, but are not limited to, those prepared by adding a copolymer selected from the group consisting of ethylene-propylene rubber (EPR), Ethylene Propylene Diene Monomer (EPDM), polyethylene, and plastomer to a polypropylene homopolymer or polypropylene random copolymer. In such polypropylene impact copolymers, the copolymer may be present in any suitable amount, but is generally present in an amount of from about 5 to about 25 weight percent. The polyolefin polymers described above may be branched or crosslinked, such as by the addition of additives that increase the melt strength of the polymer.

In an alternative embodiment of the process, the thermoplastic polymer may be replaced by or used in combination with a suitable wax. In such embodiments, the process of the present invention may be used to prepare a wax-containing additive composition or masterbatch that is used as a carrier for the cis-1, 2-cyclohexanedicarboxylic acid calcium salt and is intended for further addition to the polymer. Suitable waxes include, but are not limited to, those selected from the group consisting of animal waxes, vegetable waxes, paraffin waxes, microcrystalline waxes, polyolefin waxes, fischer-tropsch waxes, and mixtures thereof. The selection of a suitable wax for use in the composition may be influenced by the polymer to which the composition is to be added and/or the properties of the polymer composition. For example, the melting point of the wax is preferably less than or equal to the melting point of the target polymer or the polymer to be nucleated in the target polymer composition. This will ensure that the wax melts during processing to produce a molten liquid that can be thoroughly and homogeneously mixed with the target polymer, which in turn thoroughly and homogeneously disperses the nucleating agent throughout the polymer. Thus, the selection of a suitable wax for the composition may depend, at least in part, on the particular polymer to be nucleated and the melting point of that polymer. Furthermore, the selection of a suitable wax may also depend on the application or applications for which the polymer is intended. For example, if the polymer is intended for use in food contact applications, the wax is preferably one that has been deemed safe for use in such food contact applications.

The additive composition can be combined with the thermoplastic polymer in any suitable amount. Preferably, the additive composition is present in the mixture in an amount of about 50ppm or more based on the total weight of the mixture. More preferably, the additive composition is present in the mixture in an amount of about 100ppm or more, about 200ppm or more, about 250ppm or more, about 300ppm or more, about 400ppm or more, or about 500ppm or more, based on the total weight of the mixture. In a further preferred embodiment, the additive composition is present in the mixture in an amount of about 10,000ppm or less based on the total weight of the mixture. More preferably, the additive composition is present in the mixture in an amount of about 9,000ppm or less, about 8,000ppm or less, about 7,000ppm or less, about 6,000ppm or less, about 5,000ppm or less, about 4,000ppm or less, about 3,000ppm or less, or about 2,500ppm or less, based on the total weight of the mixture. Thus, in a series of preferred embodiments, the additive composition is present in the mixture in an amount of from about 50ppm to about 10,000ppm (e.g., about 100ppm to about 10,000ppm), from about 50ppm to about 5,000ppm, from about 100ppm to about 5,000ppm, from about 200ppm to about 4,000ppm, or from about 250ppm to about 3,000ppm, based on the total weight of the mixture.

In another embodiment, the polymer composition prepared by the method may be a masterbatch composition comprising a relatively large amount of the additive composition and intended to be added to other polymers to prepare a finished polymer composition comprising the desired final loading level of the additive composition. In such embodiments, the additive composition can be present in the mixture in any suitable amount. In one embodiment, the additive composition is preferably present in the mixture in an amount of about 1% by weight or more based on the total weight of the mixture. More preferably, the additive composition is present in the mixture in an amount of about 2 wt% or more, about 3 wt% or more, about 4 wt% or more, or about 5 wt% or more, based on the total weight of the mixture. In such embodiments of making the masterbatch composition, the additive composition is preferably present in the mixture in an amount of about 50 wt% or less, about 40 wt% or less, about 30 wt% or less, about 20 wt% or less, about 15 wt% or less, or about 10 wt% or less, based on the total weight of the mixture. Thus, in a series of preferred embodiments of making a masterbatch composition, the additive composition is present in an amount of from about 1 wt% to about 50 wt% (e.g., from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 15 wt%, or from about 1 wt% to about 10 wt%), from about 2 wt% to about 50 wt% (e.g., from about 2 wt% to about 40 wt%, from about 2 wt% to about 30 wt%, from about 2 wt% to about 20 wt%, from about 2 wt% to about 15 wt%, or from about 2 wt% to about 10 wt%), from about 3 wt% to about 50 wt% (e.g., from about 3 wt% to about 40 wt%, from about 3 wt% to about 30 wt%, from about 3 wt% to about 20 wt%, from about 3 wt% to about 15 wt%, or about 3 wt% to about 10 wt%), about 4 wt% to about 50 wt% (e.g., about 4 wt% to about 40 wt%, about 4 wt% to about 30 wt%, about 4 wt% to about 20 wt%, about 4 wt% to about 15 wt%, or about 4 wt% to about 10 wt%), or about 5 wt% to about 50 wt% (e.g., about 5 wt% to about 40 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%) is present in the mixture.

It is believed that most of the nucleation of the additive composition is dependent upon the concentration of the calcium salt of cis-1,2-cyclohexane dicarboxylate present in the mixture. Thus, the amount of additive composition combined with the thermoplastic polymer may alternatively be expressed by stating the concentration of the calcium salt of cis-1,2-cyclohexane dicarboxylate in the mixture. Preferably, the cis-1, 2-cyclohexanedicarboxylic acid calcium salt is present in the mixture in an amount of about 50ppm or more based on the total weight of the mixture. More preferably, the calcium salt of cis-1,2-cyclohexanedicarboxylate is present in the mixture in an amount of about 100ppm or more, about 200ppm or more, about 250ppm or more, about 300ppm or more, about 400ppm or more, or about 500ppm or more, based on the total weight of the mixture. In another preferred embodiment, the cis-1, 2-cyclohexanedicarboxylic acid calcium salt is present in the mixture in an amount of about 10,000ppm or less based on the total weight of the mixture. More preferably, the calcium salt of cis-1,2-cyclohexanedicarboxylate is present in the mixture in an amount of about 9,000ppm or less, about 8,000ppm or less, about 7,000ppm or less, about 6,000ppm or less, about 5,000ppm or less, about 4,000ppm or less, about 3,000ppm or less, or about 2,500ppm or less, based on the total weight of the mixture. Thus, in a series of preferred embodiments, the cis-1, 2-cyclohexanedicarboxylic acid calcium salt is present in the mixture in an amount of from about 50ppm to about 10,000ppm (e.g., from about 100ppm to about 10,000ppm), from about 50ppm to about 5,000ppm, from about 100ppm to about 5,000ppm (e.g., from about 100ppm to about 4,000ppm, from about 100ppm to about 3,000ppm, from about 100 to about 2,500ppm, or from about 100ppm to about 2,000ppm), from about 200ppm to about 4,000ppm (e.g., from about 200ppm to about 3,000ppm), or from about 250ppm to about 3,000ppm, based on the total weight of the mixture.

The masterbatch composition prepared by this method may comprise any suitable amount of the cis-1,2-cyclohexanedicarboxylate calcium salt. In one embodiment, the calcium salt of cis-1,2-cyclohexanedicarboxylate is preferably present in the mixture in an amount of about 0.5 weight percent or more based on the total weight of the mixture. More preferably, the additive composition is present in the mixture in an amount of about 1 wt% or more, about 1.5 wt% or more, about 2 wt% or more, about 2.5 wt% or more, about 3 wt% or more, about 4 wt% or more, or about 5 wt% or more, based on the total weight of the mixture. In such embodiments of making the masterbatch composition, the calcium salt of cis-1,2-cyclohexanedicarboxylate is present in the mixture in an amount of about 50 wt.% or less, about 40 wt.% or less, about 30 wt.% or less, about 20 wt.% or less, about 15 wt.% or less, about 10 wt.% or less, about 7.5 wt.% or less, or about 5 wt.% or less, based on the total weight of the mixture. Thus, in a series of preferred embodiments for preparing the masterbatch composition, the calcium salt of cis-1,2-cyclohexanedicarboxylate is preferably present in an amount of from about 0.5 wt.% to about 50 wt.% (e.g., from about 0.5 wt.% to about 40 wt.%, from about 0.5 wt.% to about 30 wt.%, from about 0.5 wt.% to about 20 wt.%, from about 0.5 wt.% to about 15 wt.%, from about 0.5 wt.% to about 10 wt.%, from about 0.5 wt.% to about 7.5 wt.%, or from about 0.5 wt.% to about 5 wt.%), from about 1 wt.% to about 50 wt.% (e.g., from about 1 wt.% to about 40 wt.%, from about 1 wt.% to about 30 wt.%, from about 1 wt.% to about 20 wt.%, from about 1 wt.% to about 15 wt.%, from about 1 wt.% to about 10 wt.%, from about 1 wt.% to about 7.5 wt.%, or from about 1 wt.% to about 5 wt.%), based on the total weight of the mixture, from about 1.5% to about 50% (e.g., from about 1.5% to about 40%, from about 1.5% to about 30%, from about 1.5% to about 20%, from about 1.5% to about 15%, from about 1.5% to about 10%, from about 1.5% to about 7.5%, or from about 1.5% to about 5%), from about 2% to about 50% (e.g., from about 2% to about 40%, from about 2% to about 30%, from about 2% to about 20%, from about 2% to about 15%, from about 2% to about 10%, from about 2% to about 7.5%, or from about 2% to about 5%), from about 2.5% to about 50% (e.g., from about 2.5% to about 40%, from about 2.5% to about 5%, or from about 2% to about 5%, about 2.5 wt% to about 10 wt%, about 2.5 wt% to about 7.5 wt%, or about 2.5 wt% to about 5 wt%, about 3 wt% to about 50 wt% (e.g., about 3 wt% to about 40 wt%, about 3 wt% to about 30 wt%, about 3 wt% to about 20 wt%, about 3 wt% to about 15 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 7.5 wt%, or about 3 wt% to about 5 wt%), about 4 wt% to about 50 wt% (e.g., about 4 wt% to about 40 wt%, about 4 wt% to about 30 wt%, about 4 wt% to about 20 wt%, about 4 wt% to about 15 wt%, about 4 wt% to about 10 wt%, about 4 wt% to about 7.5 wt%, or about 4 wt% to about 5 wt%), or about 5 wt% to about 50 wt% (e.g., about 5 wt% to about 40 wt%, from about 5 wt.% to about 30 wt.%, from about 5 wt.% to about 20 wt.%, from about 5 wt.% to about 15 wt.%, from about 5 wt.% to about 10 wt.%, from about 5 wt.% to about 7.5 wt.%, or from about 5 wt.% to about 5 wt.%) is present in the mixture.

In addition to the additive composition described above, the polymer composition prepared by the process may also comprise other components. Suitable additional components include, but are not limited to, antioxidants (e.g., phenolic antioxidants, phosphite antioxidants, and combinations thereof), antiblock agents (e.g., amorphous silica and diatomaceous earth), pigments (e.g., organic pigments and inorganic pigments) and other colorants (e.g., dyes and polymeric colorants), fillers and reinforcing agents (e.g., glass fiber, talc, calcium carbonate, and basic magnesium sulfate whiskers), nucleating agents, clarifying agents, acid scavengers (e.g., hydrotalcite-like acid scavengers [ e.g., from Kisuma Chemicals ]Fatty acid metal salts [ e.g. stearic acid metal salts]And metal salts of fatty acid esters [ e.g. lactates]Polymer processing additives (e.g., fluoropolymer processing aids), polymeric crosslinkers, slip agents (e.g., fatty acid amide compounds derived from the reaction between fatty acids and ammonia or amine-containing compounds), fatty acid ester compounds (e.g., fatty acid ester compounds derived from the reaction between fatty acids and hydroxyl-containing compounds such as glycerol, diglycerol, and combinations thereof), and combinations thereof.

It is believed that the polymer compositions prepared by the methods described herein can be used to prepare a variety of thermoplastic articles. The polymer composition can be formed into the desired thermoplastic article by any suitable technique, such as injection molding, injection rotational molding, blow molding (e.g., injection blow molding, injection stretch blow molding, extrusion blow molding, or compression blow molding), extrusion (e.g., sheet extrusion, film extrusion, cast film extrusion, or foam extrusion), thermoforming, rotational molding, film blowing (blown film), film casting (cast film), and the like.

The polymer compositions prepared by the methods described herein can be used to prepare any suitable article or product. Suitable products include, but are not limited to, medical devices (e.g., pre-filled syringes for retort applications, intravenous supply containers, and blood collection equipment), food packaging, liquid containers (e.g., containers for beverages, pharmaceuticals, personal care compositions, shampoos, and the like), body garments, microwavable articles, shelves, cabinet doors, mechanical parts, automotive parts, sheets, tubing (pipe), piping (tube), rotomolded parts, blow molded parts, films, fibers, and the like.

The following examples further illustrate the above subject matter, but, of course, should not be construed as in any way limiting its scope.

Example 1

This example demonstrates the improvement in physical properties achieved using the additive composition according to the invention.

Polymer compositions were prepared by weighing the specified amounts of additives into a 3kg Pro-fax 6301 polypropylene homopolymer powder batch (LyondellBasell), high-intensity mixing the combined ingredients, and extruding the resulting mixture into pellets on a single-screw extruder. Each polymer composition contained 500ppm of1010(BASF), 1,000ppm168 Secondary antioxidant (BASF) and 400ppm calcium stearate as an acid scavenger. Except for the control polyIn addition to the compound compositions, each polymer composition also contained anhydrous calcium cis-1,2-cyclohexanedicarboxylate or calcium cis-1,2-cyclohexanedicarboxylate monohydrate in the amounts shown in table 1 below. The resulting pellets were injection molded to produce test samples for physical property testing. In particular, the polymer composition was evaluated for peak polymer recrystallization temperature, haze% according to ASTM Standard D1003(50 mil plaques), flexural modulus according to ASTM Standard D790, chordwise modulus according to ISO Standard 178 and MD/TD shrinkage according to ISO Standard 294.

TABLE 1 content of anhydrous calcium cis-1,2-cyclohexanedicarboxylate (anhydrous CaCCHD) and calcium cis-1,2-cyclohexanedicarboxylate monohydrate (CaCCHD hydrate) for the control and samples 1A-1H.

Sample (I)	Anhydrous CaCCHD (ppm)	CaCCHD monohydrate (ppm)
			Reference substance	--	--
1A	330	--
			1B	660	--
1C	--	165
			1D	--	330
1E	--	495
			1F	--	660
1G	--	990
			1H	--	1,320

TABLE 2 Peak Polymer recrystallization temperatures for samples 1A, 1C, 1D, 1F, and 1G.

Sample (I)	Tc(℃)
		1A	123.5
1C	124.67
		1D	124.33
1F	125.67
		1G	126.5

As can be seen from the data in table 2, samples 1C, 1D, 1F and 1G (all comprising cis-1,2-cyclohexanedicarboxylate monohydrate) exhibited higher peak polymer crystallization temperatures than sample 1A (comprising anhydrous cis-1, 2-cyclohexanedicarboxylate). For example, the peak polymer recrystallization temperature of sample 1C was more than 1 degree celsius above that of sample 1A, which is very significant when considering the fact that sample 1C contains only half the amount (by weight) of the calcium salt of cis-1,2-cyclohexane dicarboxylic acid of sample 1A. (in fact, because the molecular weight of the calcium cis-1,2-cyclohexanedicarboxylate monohydrate is higher, the molar amount of the calcium cis-1,2-cyclohexanedicarboxylate monohydrate will be less than half). These data indicate that calcium cis-1,2-cyclohexanedicarboxylate monohydrate is a more effective nucleating agent than anhydrous calcium cis-1, 2-cyclohexanedicarboxylate. In addition, these differences in polymer recrystallization temperatures are very important for those using plastics, as higher crystallization temperatures allow parts to be removed from the mold earlier, thereby reducing cycle time and increasing process throughput.

TABLE 3 1% secant modulus (ASTM) and chordwise modulus (ISO) for control and samples 1A-1H.

Sample (I)	1% secant modulus (MPa)	Chordwise modulus (MPa)
			Reference substance	1377.6	1330.3
1A	1524.6	1506.2
			1B	1535.9	1525.7
1C	1522.9	1505.9
			1D	1542.1	1533.3
1E	1563.9	1544.8
			1F	1572.9	1555.6
1G	1594.9	1572.9
			1H	1618.6	1586.4

As can be seen from the data in Table 3, samples 1D-1H both exhibited a significant increase in secant modulus and chordwise modulus compared to samples 1A and 1B. For example, sample 1D exhibited a secant modulus approximately 20MPa higher and a chordwise modulus approximately 30MPa higher than that of sample 1A. Sample 1E exhibited a secant modulus that was approximately 30MPa higher than that exhibited by sample 1B. Further, sample 1C exhibited almost the same secant modulus and chordwise modulus as that exhibited by sample 1A. As described above, this is significant in view of the smaller amount of the cis-1, 2-cyclohexanedicarboxylic acid calcium salt present in sample 1C compared to sample 1A. Also, applicants believe that these data indicate that calcium cis-1,2-cyclohexanedicarboxylate monohydrate is a more effective nucleating agent than anhydrous calcium cis-1, 2-cyclohexanedicarboxylate.

TABLE 4 Machine Direction (MD) shrinkage, Transverse Direction (TD) shrinkage, and isotropy for the control and samples 1A-1H.

Sample (I)	MD shrinkage (%)	TD shrinkage (%)	Isotropy
				Reference substance	1.27	1.28	0.99
1A	1.21	1.2	1
				1B	1.2	1.18	1.01
1C	1.15	1.2	0.96
				1D	1.14	1.18	0.97
1E	1.12	1.16	0.97
				1F	1.14	1.15	0.99
1G	1.12	1.13	0.99
				1H	1.12	1.12	1

As noted above in the detailed description, shrinkage of the polymer composition is an important factor to consider when making parts from the polymer composition. Polymer compositions that exhibit a significant amount of shrinkage or non-uniform (anisotropic) shrinkage may experience undesirable warpage or deformation when molded into parts. Even if such parts do not warp or deform immediately after molding, the residual stresses present in the parts due to shrinkage can deleteriously affect their performance in use. Furthermore, as mentioned above, shrinkage is also related to thermal expansion, wherein polymer compositions/parts exhibiting low shrinkage also exhibit low thermal expansion.

As can be seen from the data set forth in Table 4, all of the polymer compositions made with calcium cis-1,2-cyclohexanedicarboxylate monohydrate (samples 1C-1H) exhibited less shrinkage in the machine direction than the polymers made with anhydrous calcium cis-1,2-cyclohexanedicarboxylate (samples 1A and 1B). Furthermore, all polymer compositions made with calcium cis-1,2-cyclohexanedicarboxylate monohydrate, except for sample 1C, exhibited lower transverse shrinkage than polymer compositions made with anhydrous calcium cis-1,2-cyclohexanedicarboxylate (samples 1A and 1B). As described above, the performance of sample 1C is significant in view of the fact that a lesser amount of the cis-1, 2-cyclohexanedicarboxylic acid calcium salt is present in sample 1C as compared to sample 1A. Furthermore, the improved shrinkage of samples 1C-1H does not come at the expense of reduced isotropy. Although the isotropy of samples 1C-1G is lower than that of samples 1A and 1B, the values are still close enough to unity to be considered as being isotropic in nature. These data indicate that calcium cis-1,2-cyclohexanedicarboxylate monohydrate is an effective nucleating agent for significantly reducing both the machine and transverse shrinkage of the polymer (even relative to a similar polymer composition comprising anhydrous calcium cis-1, 2-cyclohexanedicarboxylate). These data also show that this reduced shrinkage remains substantially isotropic. Finally, the reduced shrinkage exhibited by polymer compositions prepared with calcium cis-1,2-cyclohexanedicarboxylate monohydrate should also exhibit significantly less thermal expansion than the original resin or a similar polymer composition comprising anhydrous calcium cis-1, 2-cyclohexanedicarboxylate. Thus, it is believed that the additive composition of the present invention is particularly suitable for use in applications requiring parts to remain dimensionally stable with temperature changes, such as automotive trim applications (e.g., bumpers).

All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the subject matter of the application (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to,") unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.

Preferred embodiments of the subject matter of the present application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, this disclosure covers any combination of the above-described elements in all possible variations thereof unless otherwise indicated herein or otherwise clearly contradicted by context.