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Publication numberUS20060079613 A1
Publication typeApplication
Application numberUS 11/078,003
Publication dateApr 13, 2006
Filing dateMar 11, 2005
Priority dateOct 13, 2004
Also published asCN101065434A, CN101065434B, DE602005012600D1, EP1819765A1, EP1819765B1, US7879933, US20090054598, WO2006044186A1
Publication number078003, 11078003, US 2006/0079613 A1, US 2006/079613 A1, US 20060079613 A1, US 20060079613A1, US 2006079613 A1, US 2006079613A1, US-A1-20060079613, US-A1-2006079613, US2006/0079613A1, US2006/079613A1, US20060079613 A1, US20060079613A1, US2006079613 A1, US2006079613A1
InventorsRob Hanssen
Original AssigneeRob Hanssen
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Blended nucleating agent compositions and methods
US 20060079613 A1
Abstract
Certain thermoplastic additives that induce simultaneous good material properties and high nucleation efficacy are provided. Such additives include combinations of a phosphate salt and a dicarboxylate salt. This combination or blend may be provided in various ratios. A method for applying such a combination in a thermoplastic formulation is also disclosed. A thermoplastic formulation, which may or may not include polypropylene, is also disclosed in connection with the combination.
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Claims(50)
1. A blended nucleating or clarifying composition for thermoplastics comprising a blend of more than one species of nucleating agent, said blend comprising at least the following:
(a) a first nucleating agent of a carboxylic acid salt compound; and
(b) a second nucleating agent of a phosphate-containing salt compound.
2. The blended composition of claim 1 wherein said first nucleating agent is selected from the group conforming with the structure of Formula (I)
wherein M1 and M2 are the same or different, or M1 and M2 are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxyl, C1-C9 alkoxy, C1-C9 alkyleneoxy, amine, and C1-C9 alkylamine, halogen, phenyl, alkylphenyl, and C1-C9 carbocyclic.
3. The composition of claim 2 wherein said metal or organic cation is a metal cation selected from the group consisting of: Group I and Group II metal ions.
4. The composition of claim 2 wherein said metal or organic cation is selected from the group consisting of: sodium, potassium, calcium, lithium, rubidium, barium, magnesium, and strontium, silver, zinc, aluminum.
5. The composition of claim 4 wherein said metal or organic cation comprises sodium or calcium.
6. A thermoplastic article comprising the blended composition of claim 1.
7. A thermoplastic article comprising the blended composition of claim 2.
8. A thermoplastic article comprising the blended composition of claim 3.
9. A thermoplastic article comprising the blended composition of claim 4.
10. A thermoplastic article comprising the blended composition of claim 5.
11. The article of claim 6 wherein said thermoplastic article comprises polypropylene.
12. The article of claim 7 wherein said thermoplastic article comprises polypropylene.
13. The article of claim 8 wherein said thermoplastic article comprises polypropylene.
14. The article of claim 9 wherein said thermoplastic article comprises polypropylene.
15. The article of claim 10 wherein said thermoplastic article comprises polypropylene.
16. A blended nucleating or clarifying composition for thermoplastics comprising a blend of more than one species of nucleating agent, said blend comprising at least the following:
(a) a first nucleating agent of a carboxylic acid salt compound; said first nucleating agent being selected from the group conforming with the structure of Formula (I)
wherein M1 and M2 are the same or different, or M1 and M2 are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxyl, C1-C9 alkoxy, C1-C9 alkyleneoxy, amine, and C1-C9 alkylamine, halogen, phenyl, alkylphenyl, and C1-C9 carbocyclic; and
(b) a second nucleating agent of a Bis-phenol phosphate.
17. The composition of claim 16, wherein said Bis-phenol phosphate comprises the formula:
wherein: R is selected from the group consisting of: a carbon-to-carbon bond; thio sulfur —S—; and alkylidene
in which R3 and R4 are selected from the group consisting of hydrogen, alkyl having from one to about eighteen carbon atoms, and cycloalkyl, including cycloalkylidene in which R3 and R4 are taken together as part of a cycloalkylene ring, having from three to about twelve carbon atoms;
R1 and R2 each are selected from the group consisting of: hydrogen, alkyl having from about one to about eighteen carbon atoms; and cycloalkyl having from about 3-12 carbon atoms;
M is a metal atom selected from the group consisting of: alkali metal atoms and alkaline earth metal atoms; and
n is the valence of the metal atom M, and ranges from 1 to 2.
18. Bis-phenol phosphates according to claim 17 wherein R is alkylidene
and said R1 and R2 are both alkyl.
19. Bis-phenol phosphates according to claim 17 in which R is thio sulfur —S— and R1 and R2 are both alkyl.
20. Bis-phenol phosphates according to claim 17 in which R is a carbon-to-carbon bond and R1 and R2 are both alkyl.
21. Bis-phenol phosphates according to claim 17 in which R is cycloalkylidene and R1 and R2 are both alkyl.
22. Bis-phenol phosphates according to claim 17 in which R1 and R2 are each t-alkyl and R comprises alkylidene.
23. Bis-phenol phosphates according to claim 17 in which R is a carbon-to-carbon bond.
24. Bis-phenol phosphates according to claim 17 in which R is thio sulfur —S—.
25. Bis-phenol phosphates according to claim 17 in which R is alkylidene according to the structure:
26. Bis-phenol phosphates according to claim 25 in which R3 and R4 are both hydrogen.
27. Bis-phenol phosphates according to claim 25 in which R3 is hydrogen and R4 is alkyl.
28. Bis-phenol phosphates according to claim 25 in which R3 is hydrogen and R4 is cycloalkyl.
29. Bis-phenol phosphates according to claim 25 in which R3 and R4 are taken together as cycloalkylidene.
30. Bis-phenol phosphates according to claim 25 in which M is an alkali metal.
31. Bis-phenol phosphates according to claim 25 in which M is an alkaline earth metal.
32. Bis-phenol phosphates according to claim 25 in which M is a polyvalent metal.
33. Bis-phenol phosphates according to claim 25 in which R1 and R2 are each tertiary alkyl.
34. Bis-phenol phosphates according to claim 25 in which R1 is hydrogen and R2 is tertiary alkyl.
35. Bis-phenol phosphates according to claim 25 in which R1 is hydrogen and R2 is cycloalkyl.
36. A thermoplastic article comprising the blended composition of claim 16.
37. A thermoplastic article comprising the blended composition of claim 17.
38. A thermoplastic article comprising the blended composition of claim 18.
39. A blended nucleating or clarifying composition for thermoplastics comprising a blend of more than one species of nucleating agent, said blend comprising at least the following:
(a) a first nucleating agent of a carboxylic acid salt compound; and
(b) a second nucleating agent of a phosphate-containing salt compound;
(c) further wherein said first nucleating agent and said second nucleating agent are provided in said thermoplastic at a predetermined ratio.
40. The composition of claim 39 wherein said ratio of (a):(b) comprises about 1:10.
41. The composition of claim 39 wherein said ratio of (a):(b) comprises about 1:5.
42. The composition of claim 39 wherein said ratio of (a):(b) comprises about 1:3.
43. The composition of claim 39 wherein said ratio of (a):(b) comprises about 1:2.
44. The composition of claim 39 wherein said ratio of (a):(b) comprises about 1:1.
45. The composition of claim 40 wherein said blended composition is provided in said thermoplastic at concentration level of (a) of about 100 ppm.
46. The composition of claim 41 wherein said blended composition is provided in said thermoplastic at a concentration level of (a) of about 200 ppm.
47. The composition of claim 42 wherein said blended composition is provided in said thermoplastic at an overall concentration level of (a) of about 1500 ppm.
48. The composition of claim 43 wherein said blended composition is provided in said thermoplastic at a concentration level of (a) of about 500 ppm.
49. The composition of claim 44 wherein said blended composition is provided in said thermoplastic at a concentration level of (a) of between about 500 and about 1000 ppm.
50. A blended nucleating or clarifying composition for thermoplastics comprising a blend of more than one species of nucleating agent, said blend comprising at least the following:
(a) a first nucleating agent of a carboxylic acid salt compound; said first nucleating agent being selected from the group conforming with the structure of Formula (I)
wherein M1 and M2 are the same or different, or M1 and M2 are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxyl, C1-C9 alkoxy, C1-C9 alkyleneoxy, amine, and C1-C9 alkylamine, halogen, phenyl, alkylphenyl, and C1-C9 carbocyclic; and
(b) a second nucleating agent of a Bis-phenol phosphate, said second nucleating agent having the structure provided below:
wherein t-Bu refers to a tertiary butyl group.
Description
CROSS REFERENCE TO RELATED APPLICATIONS

This Application claims priority to U.S. Provisional Application No. 60/618,326; filed Oct. 13, 2004.

BACKGROUND OF THE INVENTION

Nucleating and clarifying agents are chemical compositions that may be added to thermoplastic polymers to facilitate formation of the polymer as it changes from molten to solid form in the process of crystallization. Such additives may assist in reducing haze of polymeric structures. Many different chemical compositions are known for this purpose. One major issue in the use of such agents is the amount or degree of clarity that the agent or additive imparts to a finished polymeric article. Reducing haze and thereby increasing clarity of such articles is a constant endeavor in the plastics industry.

In general, the use of nucleating agents is a highly unpredictable technology area. Small or slight changes in a molecular structure can drastically change the ability of a given nucleating composition to nucleate or clarify effectively a polymer composition. There is a large amount of unpredictability in the art of nucleating agents. There are many unknowns regarding the effect of a given substance on polymer morphology during recrystallization of thermoplastics.

As an example of one type of nucleator, dibenzylidene sorbitol (DBS) compounds are common nucleator compounds, particularly for polypropylene end products. Compounds such as 1,3-O-2,4-bis(3,4-dimethylbenzylidene)sorbitol (hereinafter DMDBS), available from Milliken and Company of Spartanburg, S.C., USA under the trade name Millad 3988®, provide excellent nucleation characteristics for target polypropylenes and other polyolefins. For example, of great interest is the compatibility of such compounds with different additives widely used within typical polyolefin (e.g., polypropylene, polyethylene, and the like) plastic articles.

Calcium stearate is a very popular acid neutralizer present within typical polypropylene formulations to protect the end product from catalyst residue attack. Unfortunately, many nucleator compounds exhibit undesirable reactions with such compounds within polyolefin articles. For sodium, and other metal ions, it appears that the calcium ion from the stearate transfers positions with the sodium ions of the nucleating agents, rendering the nucleating agents ineffective for their intended function. As a result, such compounds sometimes exhibit unwanted plate-out characteristics and overall reduced nucleation performance (as measured, for example) by a decrease in crystallization temperature during and after polyolefin processing.

Problems that may be encountered with the standard nucleators noted above include inconsistent nucleation due to dispersion problems, resulting in stiffness and impact variation in the polyolefin article. Substantial uniformity in polyolefin production is highly desirable because it results in relatively uniform finished polyolefin articles. If the resultant article does not contain a well-dispersed nucleating agent, the entire article itself may suffer from a lack of rigidity and low impact strength.

Furthermore, storage stability of nucleator compounds and compositions is another potential problem with thermoplastic nucleators. Nucleator compounds are generally provided in powder or granular form to the polyolefin manufacturer. Since uniform small particles of nucleating agent may be imperative to provide the requisite uniform dispersion and performance, such compounds must remain as small particles through storage. Certain nucleators, such as sodium benzoate, exhibit relatively high degrees of hygroscopicity such that the powders made therefrom hydrate easily resulting in particulate agglomeration. Such agglomerated particles may require further milling or other processing for de-agglomeration in order to achieve the desired uniform dispersion within the target thermoplastic. Furthermore, such unwanted agglomeration due to hydration may also cause feeding or handling problems for the user.

Solid bicyclo[2.2.1]heptane dicarboxylate salt-containing thermoplastic nucleating additive formulations are used and sold in the industry. Milliken and Company of Spartanburg, South Carolina distributes commercially nucleating agents of such metal salts, under the trade name HYPERFORM®. One such product is known commercially as HPN-68®, which is sold by Milliken and Company. U.S. Pat. Nos. 6,465,551; 6,559,211; 6,521,685; and 6,583,206 relate to such compounds and their use. The dicarboxylate salt is usually provided as a granular formulation, and is known as a very good nucleating agent, particularly for applications that require high crystallization temperatures (Tc).

Also of interest is the compatibility of such compounds with different additives widely used within typical polyolefin (e.g., polypropylene, polyethylene, ethylene copolymer polypropylene, (and the like) plastic articles. As noted previously, calcium stearate compatibility is particularly important. Unfortunately, many nucleators exhibit much deleterious nucleating efficacy with such compounds within polyolefin articles. In order to avoid combinations of these standard nucleators and calcium salts, other nonionic acid neutralizers, such as dihydrotalcite (DHT4-A®), sometimes are necessary for use in conjunction with such nucleators.

Other known compounds useful for nucleation include sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate (from Asahi Denka Kogyo K.K., known commercially as NA-11®), talc, and the like. Such compounds all impart high polyolefin crystallization temperatures; however, each also exhibits its own drawback for large-scale industrial applications. U.S. Pat. Nos. 4,463,113 and 5,342,868 disclose crystalline synthetic resin compositions of cyclic organophosphoric esters.

The structure that is believed to be used in connection with NA-11® is shown below:

A nucleating agent for polypropylene with a combination of positive material properties, like high Tc, low t1/2, isotropic shrinkage, and high stiffness would be highly desirable. Phosphate ester salts, like NA-11® and NA-21® (manufactured by Asahi Denka Kogyo Kabushiki Kaisha of Japan) are known to incur relatively high stiffness in injection molded articles. However, warpage caused by anisotropic shrinkage is often an undesired side effect of such materials. Such warpage is a disadvantage of using phosphate ester salts, and causes them to be undesirable in many applications.

Thus, it may be seen that each nucleating composition has its advantages and disadvantages. This has created a long-felt need in the polyolefin nucleator compound industry to provide compositions that minimize such problems and provide excellent peak crystallization temperatures for the target polyolefin. Unfortunately, it is a significant challenge to find nucleators exhibiting exceptionally high peak crystallization temperatures, low hygroscopicity, excellent thermal stability, high stiffness, and relatively low amounts of shrinkage or warpage in finished articles. For example, many nucleators cause shrinkage beyond the limits required to keep molded articles within their size specifications. Shrinkage is a significant problem in the industry. The invention disclosed herein is directed at minimizing such problems.

Blends of more than one nucleator have been tried, but are not always successful. Furthermore, this is a highly unpredictable area of the chemical arts, and there is usually no any way of knowing what will work until it is tried, and tested, and a relatively substantial amount of work is done.

U.S. Pat. No. 6,586,007 is directed to a combination of 3,4 -dimethylbenzylidene sorbitol (DBS) and p-methylbenzylidene sorbitol (mDBS). U.S. Pat. Nos. 6,521,685 and 6,585,819 are directed to additives that comprise a blend of (a) bicyclic salts, and (b) benzylidene sorbitol acetals.

BRIEF DESCRIPTION OF THE DRAWINGS

A full and enabling disclosure of this invention, including the best mode shown to one of ordinary skill in the art, is set forth in this specification. The following Figures illustrate the invention:

FIG. 1 shows a comparison of crystallization temperature and crystallization temperature half-time of homopolymer polypropylene nucleated by (1) Hyperform HPN-68® alone (2) NA-11UF® alone, as compared to the inventive blends of (3) Hyperform® HPN-68® with NA-11®;

FIG. 2 shows the difference in flexural modulus compared to control;

FIG. 3 shows results of shrinkage measurements; and

FIG. 4 depicts results of anisotropy calculations.

DETAILED DESCRIPTION OF THE INVENTION

Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in this invention without departing from the scope or spirit of the invention.

An object of the invention is to provide a thermoplastic additive composition that simultaneously induces high levels of nucleation efficiency as well as low degrees of haze (and thus excellent clarity) within target thermoplastic articles. Additionally, the invention provides a nucleator/clarifier additive composition that may be used in various polyolefin media for use in many end uses.

Accordingly, this invention is directed to a nucleating or clarifying agent composition that is a combination of a phosphate salt and a dicarboxylate salt. This combination or blend may be provided in various ratios. The invention also includes a method for applying such a combination in a thermoplastic formulation, and also the formulation containing the combination.

In general, it is widely known that a combination of two different types of nucleating agents in one plastic or thermoplastic leads to the result that one of the nucleators-overrides essentially all the effects of the other nucleating agent. This is a common and widely understood principle in the art of nucleation.

However, in the practice of the invention, surprisingly, it has been discovered that the addition of two specific types of nucleating agents (set forth herein) will change only one of the properties (stiffness). This is the case, even though the crystallization temperatures and crystallization half times of the resulting nucleated polymers are barely affected.

It would be expected that the combination of: (a) a phosphate salt nucleating agent, and (2) a dicarboxylate salt nucleating agent, (3) when combined in a single plastic or thermoplastic formulation: would not have had any significant effects upon the crystallization temperature or stiffness. However, this unexpectedly discovered highly desirable combination provides, in certain circumstances, a crystallization temperature (Tc) that is substantially higher than the Tc's of both the named single nucleators when used alone. Furthermore, the stiffness of the nucleator combination is higher or equal to the stiffness of using each alone. These are surprisingly and beneficial results, which are novel and nonobvious over known prior art nucleating agent compositions. Further, these results and these particular blends are unknown in the industry.

As used herein, the term “thermoplastic” refers generally to a polymeric material that will melt upon exposure to sufficient heat but will retain its solidified state upon cooling. “Thermoplastic” refers to plastics having crystalline or semi-crystalline morphology upon cooling after melt-formation, usually by the use of a mold or like article. Particular types of polymers contemplated within such a definition include, without limitation, polyolefins (such as polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (such as nylon), polyurethanes, polyester (such as polyethylene terephthalate), and the like (as well as any combinations thereof).

Thermoplastics have been utilized in a variety of end-use applications, including storage containers, medical devices, food packages, plastic tubes and pipes, shelving units, and the like. Such base compositions, however, must exhibit certain physical characteristics in order to permit widespread use. Specifically within polyolefins, for example, uniformity in arrangement of crystals upon crystallization is a necessity to provide an effective, durable, and versatile polyolefin article. In order to achieve such desirable physical properties, it has been known that certain compounds and compositions provide nucleation sites for polyolefin crystal growth during molding or fabrication. Generally, compositions containing such nucleating compounds crystallize at a much faster rate than un-nucleated polyolefin. Such crystallization at higher temperatures results in reduced fabrication cycle times and a variety of improvements in physical properties, such as stiffness.

Such compounds and compositions that provide faster and or higher polymer crystallization temperatures are popularly known as nucleators. Such compounds provide nucleation sites for crystal growth during cooling of a thermoplastic molten formulation.

In one embodiment of the invention, the combination comprises both a multi-cyclic phosphate salt and a metal or organic salts of saturated bicyclic dicarboxylates.

Such a method includes the steps of (a) providing a molten thermoplastic formulation; (b) introducing to such formulation and mixing therein a composition comprising at least one phosphate-containing salt and at least one dicarboxylate-containing salt, and (c) allowing the resultant composition of step “b” to cool into a thermoplastic article.

Salts of Dicarboxylates

Some particular, non-limiting examples of such novel nucleator compounds include the metal or organic salts of saturated [2.2.1]bicyclic dicarboxylates, and most preferably of these types of compounds conforming to Formula (I)


wherein M1 and M2 are the same or different, or M1 and M2 are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxyl, C1-C9 alkoxy, C1-C9 alkyleneoxy, amine, and C1-C9 alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal C1-C9 carbocyclic.

The metal cations are selected from the group consisting of calcium, strontium, barium, magnesium, aluminum, silver, sodium, lithium, rubidium, potassium, and the like. Within that scope, group I and group II metal ions are generally quite effective. Among the group I and II cations, sodium, potassium, calcium and strontium are useful, wherein sodium and calcium are very useful. Furthermore, the M1 and M2 groups may also be combined to form a single metal cation (such as calcium, strontium, barium, magnesium, aluminum, and the like). Although this invention encompasses all stereochemical configurations of such compounds, the cis configuration is preferred wherein cis-endo is one of the most preferred embodiments. The preferred embodiment polyolefin articles and additive compositions for polyolefin formulations comprising at least one of such compounds are also encompassed within this invention.

A blended nucleating or clarifying composition for thermoplastics is employed, comprising a blend of a first nucleating agent of a carboxylic acid salt compound and a second nucleating agent of a Bis-phenol phosphate. The first nucleating agent is selected from the group conforming with the structure of Formula (I)

wherein M1 and M2 are the same or different, or M1 and M2 are combined to from a single moiety, and are independently selected from the group consisting of metal or organic cations, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxyl, C1-C9 alkoxy, C1-C9 alkyleneoxy, amine, and C1-C9 alkylamine, halogen, phenyl, alkylphenyl, and C1-C9 carbocyclic.

Cyclic Phosphates

In some instances, the Bis-phenol phosphates comprise the formula:

wherein: R is selected from the group consisting of: a carbon-to-carbon bond; thio sulfur —S—; and alkylidene


in which R3 and R4 are selected from the group consisting of hydrogen, alkyl having from one to about eighteen carbon atoms, and cycloalkyl, including cycloalkylidene in which R3 and R4 are taken together as part of a cycloalkylene ring, having from three to about twelve carbon atoms; and in which R1 and R2 each are selected from the group consisting of: hydrogen, alkyl having from about one to about eighteen carbon atoms; and cycloalkyl having from about 3-12 carbon atoms. Typically, M is a metal atom selected from alkali metal atoms or alkaline earth metal atoms; and n is the valence of the metal atom M, and ranges from 1 to 2.

R is alkylidene


and R1 and R2 may be alkyl. In some embodiments, R is thio sulfur —S— and R1 and R2 are each alkyl. For some applications, R is a carbon-to-carbon bond and R1 and R2 are each alkyl. R may be cycloalkylidene and R1 and R2 may be each alkyl.

In yet other applications, R1 and R2 may be t-alkyl, and R may comprise alkylidene. R may be provided as a carbon-to-carbon bond. Bis-phenol phosphates may be employed in which R is thio sulfur —S—. R3 and R4 may be each hydrogen as well. Furthermore, R3 may be hydrogen and R4 may be alkyl. R3 may be hydrogen and R4 may be cycloalkyl. Alternatively, R3 and R4 may be taken together as cycloalkylidene. Bis-phenol phosphates may be provided in which M is an alkali metal. M may be an alkaline earth metal. M may be a polyvalent metal. R1 and R2 may be each tertiary alkyl. R1 may be hydrogen and R2 may be tertiary alkyl. R1 may be hydrogen and R2 may be cycloalkyl.

Exemplary R alkylidene include at least the following, but are not limited to the following: methylidene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sec-butylidene, tert-butylidene, amylidene, hexylidene, heptylidene, octylidene, isooctylidene, 2-ethyl hexylidene, nonylidene and decylidene; cyclohexylidene, cycloheptylidene, methyl cyclohexylidene, ethyl cyclohexylidene, and cyclooctylidene.

Exemplary R1 and R2, R3 and R4 alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

Exemplary R1 and R2, R3 and R4 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.

Exemplary M monovalent metals include Li, Na, Ki; exemplary bivalent metals include Be, Ca, Sr, Ba, Zn, and Cd; Exemplary trivalent and tetravalent metals include Al, Ge, Sn, Pb, Ti, Zr, Sb, Cr, Bi, Mo, Mn, Fe, Co and Ni. Among these metals, the alkali metals such as Li, Na and K and the alkaline earth metals such as Mg, Ca, Sr and Ba are known to be useful.

Compounds useful for nucleation in the combination of the invention include, but are not limited to, sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl)phosphate (from Asahi Denka Kogyo K.K., known commercially as NA-11®), talc, and the like. The invention may employ essentially any cyclic group having a phosphate attached. Bicylic, tricyclic, and the like may be employed, with a phosphate salt, as one example.

In one embodiment, the combination of the invention comprises both a multi-cyclic phosphate salt and organic salts of saturated bicyclic dicarboxylates.

As indicated, the structure of NA-11® is one example of a phosphate-containing nucleator that may be employed. Its structure is shown below:

This invention, in one embodiment, brings a combination of the positive aspects from both phosphate ester salts and Hyperform® HPN-68 (a product of Milliken and Company of Spartanburg, S.C., USA), being: High crystallization temperatures (substantially equal to Hyperform® HPN-68); Low crystallization half times (substantially equal to Hyperform® HPN-68); Isotropic shrinkage (between control and Hyperform® HPN-68); Shrinkage reduction (between NA-11 and Hyperform® HPN-68); High perceived stiffness (substantially equal to NA-11®).

Although polyolefins are preferred, the nucleating agents of the present invention are not restricted to polyolefins, and may also give beneficial nucleation properties to polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), as well as polyamides such as Nylon 6, Nylon 6,6, and others. Generally, many different types of thermoplastic compositions having some crystalline content may be improved with the nucleating agents of the present invention.

EXAMPLES

A series of nucleators was compounded into homopolymer polypropylene (Basell Pro-fax® 6301 NT) together with a standard stabilization package (800 ppm calcium stearate, 1500 ppm Irganox® B215). Plaques (dimensions: 50×70×3 mm3) were injection molded from the resulting compounds. Thermal properties were determined with a Perkin Elmer Diamond DSC. Mechanical properties (flexural modulus) were measured on a Lloyd LR10 tensile tester with a 500 N load cell.

Thermal Properties

The crystallization temperature was determined by heating approximately 2.5 mg sample to 220° C., keeping it at this temperature for 2 minutes to remove any thermal history, and cooling down to 50° C. at a cooling rate of 20° C./min. The peak of the crystallization exotherm is regarded as the crystallization temperature.

The crystallization half time was determined by heating approximately 5.0 mg sample to 220° C., keeping it at this temperature for 2 minutes to remove any thermal history, and cooling down to 135° C. at a cooling rate of 200° C./min. The time after which half of the sample had crystallized is regarded as the crystallization half time.

FIG. 1 shows the thermal properties measurements as a function of nucleator content. Values are provided in Table 1 below.

The results in FIG. 1 show that Hyperform® HPN-68 nucleated polypropylene samples at concentrations over 500 ppm of nucleator have higher crystallization temperatures than any of the NA-11® nucleated polymers. Blends of Hyperform HPN-68® and NA-11® nucleated polymers all have higher crystallization temperatures than the NA-11® nucleated polymers, irrespective of their composition. This is a surprising and unexpected result. The crystallization half times follow the same trends.

Mechanical Properties

The flexural modulus was determined from three-point bending force measurements on injection molded plaques (50×70×3 mm3). Measurements were carried out at 1.28 mm/minute bending speed on a 48 mm support span. The reported values are averages of five measurements after eight days of annealing at room temperature.

The results of the flexural modulus measurements are graphically depicted in FIG. 2; values are in Table 2 in the appendix. FIG. 2 shows the difference in flexural modulus compared to control. All nucleated samples have a higher flexural modulus than the control samples. However, it can be easily seen that the values for NA-11® nucleated homopolymer are significantly higher than for the Hyperform HPN-68® nucleated samples, irrespective of the concentration. Furthermore, there is a significant increase of flexural modulus with the concentration of NA-11®, while there is not for the Hyperform HPN-68® nucleated samples.

Samples in which both Hyperform® HPN-68 and NA-11 are present, have higher flexural moduli than samples with just Hyperform® HPN-68, and equal moduli compared to samples with just NA-11® in concentrations of Hyperform® HPN-68 and NA-11® combined.

Shrinkage and Shrinkage Anisotropy

Shrinkage was determined from injection molded plaques ((50×70×3 mm3) in both machine direction (MD) and transverse direction (TD). Shrinkage anisotropy is as in Formula 1. Equation 1 : anisotropy = relative  shrinkage  in TD relative  shrinkage  in MD - 1 Definition of anisotropy
Relative shrinkage is defined in Formula 2. Equation 2 relative shrinkage = L 0 - L L 0 * 100 % Definition of relative shrinkage .
Where L0 is the size of the mold, and L is the size of the plaque 2 days after injection molding.

Results of the shrinkage measurements are shown in FIG. 3; results of the anisotropy calculations are shown in FIG. 4. The values are in Table 3.

Hyperform® HPN-68 nucleated samples show the highest shrinkage in both machine direction (MD) and transverse direction (TD) and shrinkage is slightly dependent on HPN-68 concentration. Shrinkage in the NA-11 nucleated samples is different for TD and MD; in the MD, the shrinkage is lower than control, while in the TD shrinkage is equal to or higher than control. The samples containing both Hyperform® HPN-68 and NA-11® have shrinkages that are equal or slightly higher than control in both directions, but lower than the Hyperform® HPN-68 nucleated samples.

Effects on anisotropy are shown in FIG. 4.

Materials nucleated with only NA-11® have a high tendency for anisotropic shrinkage compared to control materials. This anisotropic shrinkage is not significantly dependent on the concentration of NA-11®. Materials nucleated with Hyperform® HPN-68 have a tendency to shrink more isotropically than control materials. Shrinkage induced by Hyperform® HPN-68 tends to be more isotropic by increasing the concentration of the nucleating agent.

Samples containing both Hyperform® HPN-68 and NA-11® have anisotropy values comparable or slightly higher than samples with just Hyperform HPN-68, and slightly lower or equal compared to control material.

Homopolymer polypropylene nucleated with a mixture of Hyperform® HPN-68 and NA-11® surprisingly and unexpectedly provides several beneficial properties in the polymer. These may include, but are not limited to, the following positive properties: High crystallization temperatures (may be substantially equal to Hyperform® HPN-68); Low crystallization half times (may be substantially equal to Hyperform® HPN-68); Isotropic shrinkage (between control and Hyperform® HPN-68); Shrinkage reduction (between NA-11® and Hyperform® HPN-68); High perceived stiffness (substantially equal to NA-11®).

Sheet extrusion and thermoforming are applications besides injection molding where this blend could be beneficial. The stiffness of NA-11 and isotropic shrinkage of Hyperform® HPN-68 are a highly desirable combination for both applications.

Accordingly, this invention is directed to a nucleating or clarifying agent composition that is a combination of a phosphate salt and a dicarboxylate salt. One example of the phosphate salt is the NA-11®, as shown above. However, many other phosphate salts could be used, and the invention is not limited to any particular phosphate salt. This combination or blend may be provided in various ratios. The invention also includes a method for applying such a combination in a thermoplastic formulation, and also the formulation containing the combination.

In the blends of the invention, synergistic effects are evident. That is: the Tc of combination is higher that Tc's of each component alone, although somewhat lower than hyperform at the total concentration of both:

NA-11 ® (500 ppm): 121.3° C.
HPN-68 ® (500 ppm): 123.6° C.
HPN-68 ® + NA-11 (both 500): 126.9° C.
HPN-68 ® (1000 ppm): 128.1° C.

The effect of the combination is surprisingly high, and also beneficial for many applications. As to stiffness, it is observed to be about the same as with Tc. That is, the stiffness is higher or equal than both alone, but somewhat lower or equal than NA-11® at the total concentration of both.

NA-11 ® (1000 ppm): 1695 MPa
HPN-68 ® (1000 ppm): 1623 MPa
HPN-68 + NA-11 ® (both 1000): 1727 MPa
NA-11 (2000 ppm): 1731 Mpa

Also, these values should be noted as well, set forth below.

NA-11 ® (1000 ppm): 1695 MPa
HPN-68 ® (500 ppm): 1614 MPa
HPN-68 + NA-11 ® (500 + 1000): 1710 MPa
NA-11 (1500 ppm): 1712 MPa

Example 1 Hyperform HPN-68:NA-11=500:500

To a mixture of 200 g polypropylene homopolymer fluff was added 5.0 g of Hyperform Concentrate Hi5-5 [Hi5-5 is a 5% concentrate form of Hyperform® HPN-68®, and also is a product of Milliken and Company of Spartanburg, S.C., USA]; 0.25 g of NA-11® (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B-215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 2 Hyperform® HPN-68:NA-11=100:1000

To a mixture of 200 g polypropylene homopolymer fluff was added 1.0 g of Hyperform® Concentrate Hi5-5, 0.50 g of NA-11® (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 3 Hyperform® HPN-68:NA-11=200:1000

To a mixture of 200 g polypropylene homopolymer fluff was added 2.0 g of Hyperform® Concentrate Hi5-5, 0.50 g of NA-11 (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B-215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 4 Hyperform® HPN-68:NA-11=500:1000

To a mixture of 200 g polypropylene homopolymer fluff was added 5.0 g of Hyperform® Concentrate Hi5-5, 0.50 g of NA-11® (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 5 Hyperform® HPN-68:NA-11=750:1000

To a mixture of 200 g polypropylene homopolymer fluff was added 7.5 g of Hyperform ® Concentrate Hi5-5, 0.50 g of NA-11 (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B-215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopblymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 6 Hyperform® HPN-68:NA-11=1000:1000

To a mixture of 200 g polypropylene homopolymer fluff was added 10.0 g of Hyperform® Concentrate Hi5-5, 0.50 g of NA-11 (2,2′-METHYLENE-BIS(4,6-DI-TERT-BUTYLPHENYL)PHOSPHATE SODIUM) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 7 Hyperform® HPN-68 500 ppm—Comparative

To a mixture of 200 g polypropylene homopolymer fluff was added 5.0 g of Hyperform® Concentrate Hi5-5 and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 8 Hyperform® HPN-68 1000 ppm—Comparative

To a mixture of 200 g polypropylene homopolymer fluff was added 10.0 g of Hyperform® Concentrate Hi5-5 and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 9 NA-11® 1000 ppm—Comparative

To a mixture of 200 g polypropylene homopolymer fluff was added 0.50 g of NA-11® (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene homopolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 10 Extrusion and Injection Molding

The mixtures obtained in examples 1 to 7 were melt-compounded on a Killion® KLB 100 (L/D ratio 32:1-single screw D=1″). The temperature profile was set at 205 ° C. (feed)-220° C.-230° C.-230° C. (die) and a screen pack screen pack (40/300/100/60 mesh) was used. Plaques of dimensions 70×50×3 mm3 (length×width×thickness) were injection molded from the melt-compounded blends on an Arburg Allrounder 221-55-250 with 18 mm diameter screw. The temperature profile was set as follows, 200° C. (feed)-215° C.-215° C.-215° C. (nozzle).

Example 11 Physical Testing

Crystallization temperatures were determined with a Perkin Elmer Diamond DSC on small pieces (˜2.5 mg) of injection molded plaques. The following temperature profile was used: heating at 20° C./min to 220° C., holding at 220° C. for 2 minutes, cooling at 20° C./min to 50° C. The crystallization temperature Tc was determined in the cooling run. Subsequent heating at 20° C. to 220° C. provided the melting temperature. Shrinkage was determined by measuring the injection molded 3 mm plaques 48 hours after injection molding with a caliper. Shrinkage in both machine as well as transverse direction were calculated by the formula shrinkage=(L0−L)/L0*100%, in which L0 is the mold dimension and L is the size of the injection molded plaque after 48 hours. Shrinkage anisotropy is determined by the formula anisotropy=(shrinkage TD)/(shrinkage MD)−1. Flexural modulus is determined 7 days after injection molding on 3 mm plaques.

Example 12 Hyperform® HPN-68:NA-11=500:500, Random Copolymer

To a mixture of 200 g polypropylene random copolymer fluff was added 5.0 g of Hyperform® Concentrate Hi5-5, 0.25 g of NA-11 (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene random copolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 13 Hyperform® HPN-68:NA-11=500:1000. Random Copolymer

To a mixture of 200 g polypropylene random copolymer fluff was added 5.0 g of Hyperform Concentrate Hi5-5, 0.50 g of NA-11 (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene random copolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

Example 14 Hyperform® HPN-68:NA-11=1000:1000, Random Copolymer

To a mixture of 200 g polypropylene random copolymer fluff was added 10.0 g of Hyperform® Concentrate Hi5-5, 0.50 g of NA-11 (2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate sodium) and a standard stabilization package (0.75 g Irganox® B215 and 0.40 g calcium stearate). To this mixture, enough polypropylene random copolymer fluff was added for the total weight to reach 500.00 g. The resulting mixture was physically blended with a ribbon blender for at least five minutes.

It is understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions. The invention is shown by example in the appended claims.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7589138 *Dec 5, 2006Sep 15, 2009Fina Technology, Inc.Injection molding process
US8207270Sep 29, 2006Jun 26, 2012Exxonmobil Chemical Patents Inc.blends of a propylene homo/copolymer, rubbers and crystallization agents, having superior crystallization kinetics, used as molding materials
CN101563202BDec 5, 2007Jul 25, 2012弗纳技术股份有限公司Injection molding process
WO2008085250A1 *Dec 12, 2007Jul 17, 2008Milliken & CoThermoplastic and nucleating agent compositions and methods
Classifications
U.S. Classification524/115, 524/394
International ClassificationC08K5/49, C08K5/09
Cooperative ClassificationC08K5/523, C08K5/098, C08K5/0083
European ClassificationC08K5/00P10, C08K5/098, C08K5/523
Legal Events
DateCodeEventDescription
May 17, 2006ASAssignment
Owner name: MILLIKEN & COMPANY, SOUTH CAROLINA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HANSSEN, ROB;REEL/FRAME:017863/0880
Effective date: 20050526