WO2005047383A1 - Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques - Google Patents

Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques Download PDF

Info

Publication number
WO2005047383A1
WO2005047383A1 PCT/US2004/028437 US2004028437W WO2005047383A1 WO 2005047383 A1 WO2005047383 A1 WO 2005047383A1 US 2004028437 W US2004028437 W US 2004028437W WO 2005047383 A1 WO2005047383 A1 WO 2005047383A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
concentrate
group
polyolefin
thermoplastic
Prior art date
Application number
PCT/US2004/028437
Other languages
English (en)
Inventor
Kemper David Lake, Jr.
Bhavesh Chandrakant Gandhi
Original Assignee
Milliken & Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/703,855 external-priority patent/US7078450B2/en
Priority claimed from US10/704,391 external-priority patent/US6995202B2/en
Application filed by Milliken & Company filed Critical Milliken & Company
Priority to EP04782852A priority Critical patent/EP1680464A1/fr
Publication of WO2005047383A1 publication Critical patent/WO2005047383A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3063—Magnesium sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix

Definitions

  • This invention relates to providing concentrates (also known as masterbatches) of certain bicyclic dicarboxylate salt thermoplastic nucleating additives in order to facilitate use thereof in typical thermoplastic manufacturing procedures.
  • Such nucleating additives have been found to impart high peak crystallization temperatures to thermoplastics (such as polypropylene, as one example); however, when combined in masterbatch form in the past such a nucleation property was sacrificed to a certain extent due to unforeseen problems associated with polymer-containing concentrates (i.e., pellets, for example) of such additives.
  • improvements in masterbatching of these bicyclic dicarboxylate salt thermoplastic nucleators have been accomplished to the level necessary to allow for concentrate use with concomitant effective nucleation effects at the same level (if not in excess thereof) of the utilization of such a nucleator added directly into a molten resin (i.e., not in concentrate form).
  • thermoplastic additive compositions and methods of producing thermoplastics with such nucleator additive concentrates are also contemplated within this invention.
  • Background of the Prior Art All U.S. patents cited below are herein entirely incorporated by reference.
  • thermoplastic is intended to mean a polymeric material that will melt upon exposure to sufficient heat but will retain its solidified state, but not prior shape without use of a mold or like article, upon sufficient cooling.
  • such a term is intended solely to encompass polymers meeting such a broad definition that also exhibit either crystalline or semi-crystalline morphology upon cooling after melt- formation through the use of the aforementioned mold or like article.
  • polystyrene resin such as polyethylene, polypropylene, polybutylene, and any combination thereof
  • polyamides such as nylon
  • polyurethanes such as polyurethanes
  • polyester such as polyethylene terephthalate
  • Thermoplastics have been utilized in a variety of end-use applications, including stora _/htainers, 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.
  • 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, as one example, stiffness.
  • Such compounds and compositions that provide faster and or higher polymer crystallization temperatures are thus popularly known as nucleators.
  • Such compounds are, as their name suggests, utilized to provide nucleation sites for crystal growth during cooling of a thermoplastic molten formulation. Generally, the presence of such nucleation sites results in a larger number of smaller crystals. As a result of the smaller crystals formed therein, clarification of the target thermoplastic may also be achieved, although excellent clarity is not always a result. The smaller crystal size, the less light is scattered. In such a manner, the clarity of the thermoplastic article itself can be improved. Thus, thermoplastic nucleator compounds are very important to the thermoplastic industry in order to provide enhanced clarity, physical properties and/or faster processing.
  • thermoplastic nucleator in terms of high crystallization temperatures is a saturated bicyclic dicarboxylate salt available from Milliken & Company under the tradename of HPN-68, disclosed within U.S. Pat. Nos. 6,465,551 and 6,534,574, both entirely incorporated herein by reference, along with other like saturated dicarboxylate salt nucleator compounds (HPN-68 itself is disodium bicyclo[2.2.1]heptanedicarboxylate).
  • Other measurable physical improvements such compound types impart to thermoplastics include greater stiffness and superior dimensional stability.
  • thermoplastic nucleating agents that exhibit appreciably lower crystallization temperatures, as well as less effective dimensional stability levels, etc., as compared with saturated dicarboxylate salt types, include dibenzylidene sorbitol compounds, such as 1,3-0- 2,4-bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS), available from Milliken & Company under the trade name Millad® 3988, sodium benzoate, sodium 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate (from Asahi Denka Kogyo K.K., known as NA-11), talc, cyclic bis-phenol phosphates (such as NA-21, also available from Asahi Denka), and, as
  • Such compounds all impart relatively high polyolefin crystallization temperatures; however, each also exhibits its own drawback for large-scale industrial applications, and none can match the effectiveness of the above-noted saturated types.
  • Some of the above-noted nucleating agents also provide clarifying properties within certain thermoplastics, such as polypropylene (Millad® 3988, for example, and to a lesser extent, NA-21). Such clarification capabilities coupled with high peak crystallization temperatures are highly desired.
  • the previously listed dicarboxylate salt nucleating agents unfortunately generally exhibit relatively high haze levels within polypropylene, although such compounds also provide excellent calcium stearate compatibility and increased stiffness within target thermoplastic articles. Thus, such compounds provide extremely desirable qualities and benefits within target thermoplastics.
  • thermoplastic additives are highly desirable for a number of reasons. Generally, the primary purpose for these concentrates has been to provide the end-use manufacturer with the flexibility to impart a wide variety of desirable properties to both general and specific purpose plastic polymers.
  • Such concentrates contain any number of different types of additives, such as, as merely examples, organic and inorganic colorants, inorganic fillers, antioxidants, lubricants, acid scavengers, etc., and have been utilized for many years within the plastics industry.
  • additives such as, as merely examples, organic and inorganic colorants, inorganic fillers, antioxidants, lubricants, acid scavengers, etc.
  • Such concentrates provide a highly effective delivery system of additives in order to impart any number of different properties to the subject, ultimate thermoplastic formulation and/or article.
  • imparted properties may include lubricity, protection from oxidation, protection from UV degradation, protection from corrosion, antimicrobial protection, clarity, opacity, nucleation, antiblocking performance, antistatic performance, flame retardancy, viscosity change, organoleptic enhancements, impact improvement, increased stiffness, improved dimensional stability, color, and enhancements to other optical, physical, and rheological properties.
  • lubricity protection from oxidation, protection from UV degradation, protection from corrosion, antimicrobial protection, clarity, opacity, nucleation, antiblocking performance, antistatic performance, flame retardancy, viscosity change, organoleptic enhancements, impact improvement, increased stiffness, improved dimensional stability, color, and enhancements to other optical, physical, and rheological properties.
  • Past methods of introduction within thermoplastic manufacturing procedures have basically been limited to utilization of the powder or granule form of such nucleators directly within a thermoplastic formulation and/or stream prior to melt-compounding, extrusion, molding, etc., and thus added in an amount that is at-level with the amount present within the finished article (such as, without limitation, 1500 ppm), and subsequent cooling.
  • the utilization of powders complicates manufacturing methods and makes transport and introduction relatively difficult for the user.
  • concentrates materials when primarily comprised of carrier polymer and relatively high amounts of a nucleator that, when admixed and melt-blended with target polymer resins, permit subsequent let-down of a relatively low amount of the desired concentrate within such a target resin or finished article thereof
  • a/k/a/, masterbatches such terms are well understood by the ordinarily skilled artisan within such the thermoplastics industry
  • masterbatches or concentrates have been difficult to provide for these highly desired nucleating additives to date.
  • the mere incorporation of such concentrated nucleators within pellets of polypropylene (or other like polymer) has not translated into effective high peak crystallization temperatures within the ultimate end-use article.
  • This invention allows an HPN-68 concentrate to be made with at least a 5% concentration of HPN-68 using a wider variety of carrier resins (along with a wide variety of available melt flow properties).
  • the subject concentrate is more economically attractive to use as its required usage levels will be lower than the concentrates made with HPN-68 loadings containing less than 5% HPN-68.
  • this concentrate after let-down, can provide optimum nucleation properties and associated attributes that rival those of a nucleated control (dry blended and melt compounded) containing the same at-level final product loadings of HPN-68.
  • the term "at-level” is intended to encompass the amount of nucleator present within a an article produced from a target nucleated resin wherein the nucleator was added directly to the target resin (either prior to or during melt-compounding).
  • the amount of nucleator maybe as high as 20% of that material and still result in a let-down within the target nucleated resin that provides the usual amount of nucleator required to effectuate proper nucleation if added directly (i.e., from about 1000 to about 1500 ppm, an at-level amount).
  • an object of the invention is to provide a masterbatch [concentrate of a carrier polymer and target nucleation (a/lc/a polymer morphology modifying) additives] of saturated bicyclic dicarboxylate salt nucleating agents that imparts peak crystallization temperatures of at least the same level as the neat powder form of the same nucleation agents that have been melt-compounded into the same target thermoplastic formulation.
  • an object of this invention is to provide a manner of introducing saturated bicyclic dicarboxylate salt nucleating agents in concentrate form that permits impartation of exceptional nucleation efficacy, as indicated by very high polymer peak crystallization temperatures, within polyolefin articles. Additionally, it is an object of this invention to provide thermoplastic nucleating compositions that may be used in various polyolefin media for use in myriad end- uses.
  • thermoplastic additive concentrate comprising at least one polymer constituent, at least one dispersing aid additive, and at least one saturated metal or organic salts of bicyclic dicarboxylates, preferably saturated metal or organic salts of bicyclic dicarboxylates, preferably, bicyclo[2.2.1]heptane-dicarboxylates, or, generally, compounds conforming to Formula (I)
  • Ri, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , Rg, R 9 , and R l0 are individually selected from the group consisting of hydrogen, -C 9 alkyl, hydroxy, -C 9 alkoxy, C1-C 9 alkyleneoxy, amine, and C 1 -C 9 all ylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal carbocyclic having up to nine carbon atoms
  • R' and R" are the same or different and are individually selected from the group consisting of hydrogen, C1-C 30 alkyl, hydroxy, amine, polyamine, polyoxyamine, C1-C 30 alkylamine, phenyl, halogen, Ci-C 3 Q alkoxy, C C 3 o polyoxyalkyl, C(O)-NR ⁇ C(O)O- R'", and C(O)O-R'", wherein R ⁇ is selected from the group consisting of C ⁇
  • R' and R" are the same and R'" is either Na + or combined together for both R' and R" and Ca 2+ .
  • Other possible compounds are discussed in the preferred embodiment section below.
  • a method of producing a thermoplastic article comprising the steps of (a) providing a thermoplastic polymer; (b) providing a concentrate as defined above; (c) incorporating said concentrate within said thermoplastic polymer formulation when both of said thermoplastic polymer formulation and concentrate are in molten form, thereby permitting said concentrate to melt and be mixed within said thermoplastic polymer; and (d) allowing the resultant concentrate-containing thermoplastic polymer to cool.
  • a nucleating compound within said concentrate, and ultimately within said nucleated thermoplastic polymer conforms to the structure of Formula CD)
  • Mi and M 2 are the same or different and are independently selected from the group consisting of metal or organic cations or the two metal ions are unified into a single metal ion (bivalent, for instance, such as calcium, for example), and Ri , R 2 , R 3 , R ⁇ R 5 , R 6 , R7, Rs > R 9 , and R10 are individually selected from the group consisting of hydrogen, C1-C9 alkyl, hydroxy, C1-C 9 alkoxy, C 1 -C 9 alkyleneoxy, amine, and C1-C 9 alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal carbocyclic having up to 9 carbon atoms.
  • the metal cations are selected from the group consisting of calcium, strontium, barium, magnesium, aluminum, silver, sodium, lithium, rubidium, potassium, and the like.
  • group I and group II metal ions are generally preferred.
  • sodium, potassium, calcium and strontium are preferred, wherein sodium and calcium are most preferred.
  • the Mi and M 2 groups may also be combined to form a single metal cation (such as calcium, strontium, barium, magnesium, aluminum, including monobasic aluminum, and the like).
  • this invention encompasses all stereochemical configurations of such compounds, the cis configuration is preferred wherein cis-endo is the most preferred embodiment.
  • polyolefin articles and additive compositions for polyolefin formulations comprising at least one of such compounds, broadly stated as saturated bicyclic carboxylate salts, are also encompassed within this invention.
  • saturated bicyclic dicarboxylate salt nucleators i.e., HPN-68
  • a dispersion aid additive is required to provide such results and thus ultimately permit production of high peak crystallization temperature thermoplastics through utilization of the inventive concentrates.
  • dispenser aid additive in relation to this invention is intended to encompass any compound that, when incorporated in an amount of from about 1-80% (preferably from about 2-75%, more preferably from about 5-65%, and most preferably from about 25-60%) by weight of the total pelletized concentrate, permits proper dispersion of the nucleating agent, above, in order to permit the proper impartation of the desired high peak crystallization temperatures within the target ultimate thermoplastic article.
  • examples of such an additive include metal carbonates, metal sulfates, metal talcites, metal hydrotalcites, metal dihydrotalcites, fatty acids or salts thereof, fatty acid amides, silica gels, and fatty ester-, acid- , or amide-modified samples of such metal-based compounds, and any mixtures thereof.
  • metal carbonates more preferred are stearate-modified metal carbonates, and most preferred is stearate-modified calcium carbonate.
  • At least one dispersion aid additive in an amount of from 1-80% by total weight of the concentrate, preferably from 2-75%, more preferably from 5-65%, and most preferably from 25-60%, basically in an amount that actually provides improved nucleation effects imparted by the bicyclic dicarboxylate salt nucleator within the target resin
  • the resultant thermoplastic preferably, polypropylene
  • dispersion aid additives provide effective prevention of agglomeration of the individual plate structures of the required bicyclic dicarboxylate salt nucleators. Such plate structures exhibit a propensity to accumulate and agglomerate, thus potentially deleteriously affecting the capability of such nucleators from fulfilling their desired function.
  • dispersion aid additives prevents such interaction during thermoplastic production after introduction of the inventive concentrates therein, thereby permitting the full benefits of such an effective nucleator to be realized.
  • Calcium carbonate itself is a commonly used filler in the polyolefins industry.
  • the filler may impart a polymer Tc of 117°C, ⁇ 8°C higher than the same non-nucleated resin containing no calcium carbonate filler and ⁇ 10°C lower than that which could be obtained with conventional loadings (-0.1%) of HPN-68.
  • concentrate or "masterbatch” is well-understood by the ordinarily skilled artisan within the thermoplastic resin art as a manner of providing and delivering certain additives within target resins during manufacture.
  • a concentrate may be made by any commercial process steps, including dry-blending, melt-compounding, agglomeration, compaction, extrusion, and the like, and may be present in a typical solid or liquid form, including, without limitation, granular, flake, or pelletized solid form and liquid solution, suspension, or paste (whereby the inventive formulation has been diluted with a liquid carrier in order to modify its mode of delivery), and the like, in liquid (or liquid-like) form.
  • the thermoplastic carrier may actually be substituted by a liquid medium.
  • these nucleating salts provide excellent high peak crystallization temperatures in a variety of polyolefin formulations, particularly within random copolymer polypropylene (hereinafter RCP), impact copolymer polypropylene (hereinafter ICP), homopolymer polypropylene (hereinafter HP), and polyethylene (such as low density polyethylene, linear low density polyethylene, high density polyethylene, and the like).
  • RCP random copolymer polypropylene
  • ICP impact copolymer polypropylene
  • HP homopolymer polypropylene
  • polyethylene such as low density polyethylene, linear low density polyethylene, high density polyethylene, and the like.
  • bicyclic dicarboxylate salts provide excellent mechanical properties for polyolefin articles without the need for extra fillers and rigidifying additives (although such fillers and additives may be included within target resins if desired), and desirable processing characteristics such as improved (shorter) cycle time.
  • Such salts also do not interact deleteriously with calcium stearate additives.
  • Tc polymer peak crystallization temperature
  • a key quantitative method to assess the performance of a bicyclic dicarboxylate nucleator concentrate has been to determine the polymer Tc after let-down of the concentrate into a non-nucleated resin which was subsequently injection molded into test specimens.
  • the polymer Tc determined here is then compared to the polymer Tc of a comparative sample that was prepared by incorporating the HPN-68 additive into the resin at-level via dry blending the neat nucleator powder into the polyolefin base reactor flake, melt compounding this mixture, then injection molding the same test specimens.
  • This latter preparation of the comparative sample represents what can be achieved by polyolefin producers or toll compounders.
  • Concentrates containing relatively high loadings (3-10% by weight) of bicyclic dicarboxylate nucleators have been found to produce polymer peak Tc results after let-down that are 2-4°C lower than that which can be obtained by incorporating the HPN-68 via dry blending and melt compounding into the same base resin (a/lc/a/, pre- compounded resins), both cases the final concentration of HPN-68 for each scenario would be the same, for example, 1000 ppm.
  • Such formulations may be utilized in myriad different end-uses, including without limitation, such broadly considered groups as fibers, thin film or thin-walled articles (e.g., pliable wrappers, thin-walled drinking cups, etc., having thicknesses between 0.1 and 15 mils, for example), thicker plaque or other like solid articles (e.g., from 15 to 150 mils in thickness), and even thicker-walled articles (e.g., greater than 150 mils thickness).
  • fibers e.g., thin film or thin-walled articles (e.g., pliable wrappers, thin-walled drinking cups, etc., having thicknesses between 0.1 and 15 mils, for example), thicker plaque or other like solid articles (e.g., from 15 to 150 mils in thickness), and even thicker-walled articles (e.g., greater than 150 mils thickness).
  • each group include, again, without limitation, either as complete articles, or as components of articles, the following: a) fibers: spun and nonwoven polyolefin, polyamide, polyaramid, and the like, fibers of any denier measurement, as well as blends with other synthetic or natural fibers (e.g., cotton, ramie, wool, and the like); b) thin film articles: cast films, candy wrappers, package wrappers (e.g., cigarette box wrappers, for example), and other like blown, extruded, or other similar type of film application, as well as thin-walled articles, such as drinking cups, thin containers, coverings, and the like; c) thicker plaque or other like solid articles: deli containers, water cups, cooler linings, syringes, labware, medical equipment, pipes, tubes, urinalysis cups, intravenous bags, food storage containers, waste containers, cooler housings, automotive instrument panels, flower pots, planters, office storage articles, desk storage articles, bottles, disposable packaging (
  • polyolefin or polyolefin resin is intended to encompass any materials comprised of at least one polyolefin compound.
  • Preferred examples include isotactic and syndiotactic polypropylene, polyethylene, poly(4-methyl)pentene, polybutylene, and any blends or copolymers thereof, whether high or low density in composition, as well as polyolefin-containing elastomers (such as TPVs, TPEs, and the like).
  • the polyolefin polymers of the present invention may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated co-monomers.
  • the co-monomers if present, will be provided in a minor amount, e.g., about 10 percent or less or even about 5 percent or less, based upon the weight of the polyolefin (e.g. random copolymer polypropylene), but copolymers containing up to 25% or more of the co- monomer (e.g., impact copolymers) are also envisaged.
  • Other polymers or rubber such as EPDM or EPR
  • Such co-monomers may serve to assist in clarity improvement of the polyolefin, or they may function to improve other properties of the polymer (such as impact, etc.).
  • olefin polymers whose transparency can be improved conveniently according to the present invention are polymers and copolymers of aliphatic monoolefins containing 2 to about 6 carbon atoms which have an average molecular weight of from about 10,000 to about 2,000,000, preferably from about 30,000 to about 300,000, such as, without limitation, polyethylene, linear low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, crystalline ethylenepropylene copolymer, poly(l-butene), polymethylpentene, 1-hexene, 1-octene, and vinyl cyclohexane.
  • the polyolefins of the present invention may be described as basically linear, regular polymers that may optionally contain side chains such as are found, for instance, in conventional low density polyethylene.
  • the nucleating agent concentrates of the present invention are not restricted to introduction within 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.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • any thermoplastic composition having some crystalline content may be improved with the nucleating agent concentrates of the present invention.
  • polymer foams such as, as one non-limiting example, polypropylene foams
  • wood-filled thermoplastics are also contemplated as target resins within this invention.
  • the polymer constituent of the concentrate is not required to be the same as the target thermoplastic to which the concentrate is added.
  • the concentrate polymer may exhibit any such characteristics as compared with the polymer of the target to-be-nucleated thermoplastic without incident.
  • such concentrate polymer will at least be of the same chemical structure as the target thermoplastic (i.e., polypropylene concentrate added to a molten polypropylene resin), in order to provide more reliable physical results.
  • the target thermoplastic i.e., polypropylene concentrate added to a molten polypropylene resin
  • Another potentially preferred example includes the utilization of impact copolymer (ICP), such as polypropylene ICP, as the concentrate polymer constituent for introduction within random copolymer (RCP), such as RCP polypropylene, ICP polypropylene, or polypropylene HP.
  • ICP impact copolymer
  • RCP random copolymer
  • polyethylene is a polyethylene as the concentrate polymer constituent for introduction within a polypropylene or impact copolymer polypropylene target resin.
  • compositions of the present invention may be obtained by mixing and melt- extruding the aforementioned dispersion aid additive plus saturated bicyclic dicarboxylic salt (or combination of salts or composition comprising such salts) plus molten polymer constituent, allowing such a resultant formulation to cool, and slicing the resultant polymer into pellets.
  • the desired thermoplastic polymer or copolymer can then be produced by introducing the concentrate therein (while the thermoplastic is in molten form or blending pellets of thermoplastic and concentrate first), and mixing and melt-extruding (or other polymer formation procedure) the resultant molten concentrate-containing thermoplastic, followed by cooling thereof.
  • the concentrate may contain other additives, such as antioxidants, lubricants, antistatic agents, ultraviolet absorbers, antimicrobial compounds and/or formulations, acid scavengers, polyolefin (e.g., polyethylene) waxes, stearate esters of glycerin, montan waxes, mineral oil, pigments, clarifying agents, other nucleators, and the like.
  • additives such as antioxidants, lubricants, antistatic agents, ultraviolet absorbers, antimicrobial compounds and/or formulations, acid scavengers, polyolefin (e.g., polyethylene) waxes, stearate esters of glycerin, montan waxes, mineral oil, pigments, clarifying agents, other nucleators, and the like.
  • Air-jet milling of the bicyclic nucleator either by itself, or together with the dispersion aid additive, within the ultimate concentrate formulation has also been found to impart lower haze/increased peak crystallization temperature for target thermoplastic articles
  • the target thermoplastic composition may then be processed and fabricated by any number of different techniques, including, without limitation, injection molding, injection blow molding, injection stretch blow molding, rotational molding, compression molding, extrusion, extrusion blow molding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, thermoforming, film-forming (such as into blown-films, biaxially oriented films, and the like), thin wall injection molding, polymer foams (polypropylene foams, for example) and the like, into a fabricated article.
  • Preferred Embodiments of the Invention This invention can be further elucidated through the following examples where examples of particularly preferred embodiment within the scope of the present invention are presented.
  • Spray drying was accomplished via a spray dryer using a rotary atomizer having an atomizer speed set at 9600 rpm with the inlet temperature set at 400°F ( ⁇ 204-205°C), and the outlet temperature kept between 220-225°F (-104- 108°C).
  • NMR and IR analyses were consistent with that of the expected structure of disodium bicyclo[2.2. l]heptane-2,3-dicarboxylate (hereinafter referred to as HPN-68).
  • Non-Nucleated Resins To test the performance of an experimental nucleator concentrate, the concentrate was let-down into a non-nucleated resin for subsequent blending of the mixture, injection molding of the mixture, and thermal analysis (polymer peak Tc) of the mixture. Unless otherwise indicated, a reactor grade flake was blended with a basic stabilization package on a low intensity Hobart A200 mixer using a flat beater attachment.
  • the basic stabilization package consisted of a hindered phenol type primary antioxidant (0.05% of IRGANOX® 1010), a phosphite type secondary antioxidant (0.10% of IRGAFOS® 168), and a calcium stearate acid monralizer (0.05% HYQUAL® 5853-90).
  • the batch size was 3 kg and the low intensity blend time was 5 minutes with an agitator speed of 61 rpm and a beater speed of 107 rpm.
  • the non-nucleated blends were then melt compounded on an MPM 38 mm single screw extruder having a length to diameter ratio of 24:1 and containing a Maddocks mixer.
  • the zone temperatures of the extruder were ramped from 204°C at the throat to 232°C at the die. Screw speed was controlled at 130 rpm.
  • the extrudate was filtered with a 60 mesh screen pack then passed through a 4 strand die, into a water bath, then into a pelletizer where the solidified strands were chopped into processible pellets.
  • a reactor grade flake or granule was blended with a basic stabilization package, a high loading of nucleator as indicated in the following Experimental Tables 1-9, and also other various additives that were evaluated in various concentrations as enhancers to the performance of the subject nucleator when delivered from the concentrate (also referenced in the aforementioned Experimental Tables).
  • the basic stabilization package unless otherwise indicated, consisted of a hindered phenol type of primary antioxidant (0.05% Irganox 1010), a phosphite type secondary antioxidant (0.10% of Irgafos 168), and a calcium stearate acid monralizer (0.05% HyQual 5853-90).
  • the batch size was 0.5 kg and this mixture was blended on a 4 liter Merlin high intensity mixer for 2 minutes @ 2100 rpm.
  • the blended concentrate mixture was then melt compounded on a Prism corotating twin screw extruder having a screw diameter of 16 mm and a length to diameter ratio of 25 : 1.
  • the extruder barrel temperature was controlled with the following setpoints: zone 1 - 195°C, zone 2 - 200°C, zone 3 - 205°C, zone 4 - 215°C, and die - 200°C.
  • Extruder screw rotation was controlled at 500 rpm and the feeder of the blended concentrate was set between 90-130 in order to control the torque of the extruder between 19.5-21.5 Newton meters.
  • nucleator concentrates were let-down (i.e. 2% or 50:1) into the non-nucleated resin samples at the appropriate loading to deliver the final desired concentration (i.e. 0.1 %) of nucleator (i.e. HPN-68).
  • the pelletized mixture was blended on a Kitchenaid Classic mixer using a metal whip mixing attachment. The samples were blended for 5 minutes with an agitator speed of 107 rpm and a mixing whip speed of
  • the samples were injection molded on an Arburg 40 ton press into test plaques having dimensions of 50.8 mm x 76.2 mm x 1.27 mm.
  • the injection molder barrel temperature was controlled with a flat 230°C profile while the mold temperature was controlled at 25°C.
  • the molder contained a 25 mm general purpose screw having a length to diameter ratio of 25 : 1.
  • a back pressure of -250 bar was applied to the molten polymer during the screw recovery phase of the cycle! The total molding cycle was -28 seconds.
  • Nucleated controls were prepared as a point of comparison for the concentrate after being let-down into a non-nucleated resin (previously described). Unless otherwise indicated in the previous tables, a reactor grade flake (or granule) was blended with a basic stabilization package and the comparative final target loading (i.e. 0.1 %) of nucleator.
  • the basic stabilization package unless otherwise noted, consisted of a hindered phenol type primary antioxidant (0.05% Irganox 1010), a phosphite type secondary antioxidant (0.10% of Irgafos 168), and a calcium stearate acid monralizer (0.05% HyQual 5853-90).
  • the batch size was 1 kg and the mixtures were dry blended on a 4 liter Merlin high intensity mixer for 1 minute at 2100 rpm. These blends were subsequently melt compounded on a Killion 25 mm single screw extruder having a length to diameter ratio or 24: 1 and containing a Maddocks mixer. Screw speed was 110 rpm.
  • the extrudate was filtered through a 60 mesh screen pack and passed through a single strand die, into a water bath, and subsequently into a pelletizer where the solidified strand was chopped into processible pellets.
  • the compounded pellets were then injection molded on an Arburg 40 ton press into test plaques having dimensions of 50.8 mm x 76.2 mm x 1.27 mm.
  • the injection molder barrel temperature was controlled with a flat 230°C profile while the mold temperature was controlled at 25°C.
  • the molder contained a 25 mm general purpose screw having a length to diameter ratio of 25 : 1.
  • the total inj ection molding cycle was -28 seconds.
  • Tc Polymer peak crystallization temperature
  • the concentrate carrier resin was a 20 MFR polypropylene medium impact copolymer to which the weight percent as noted within the table of the nucleator salt of the above example, was added when in molten form and thoroughly mixed therein.
  • the resultant concentrate was then extruded and ultimately formed into pellets as noted above.
  • the concentrate was then let-down into a 12 MFR polypropylene homopolymer when in molten form, mixed thoroughly, then cooled (in a molded form) to form a thermoplastic plaque.
  • Thermoplastic compositions plaque were produced comprising the initial concentrates noted above in the manner described previously.
  • the sample thermoplastic was a 12 MFR homopolymer polypropylene (HP) for the following Experimental Tables unless otherwise noted. Testing for nucleating effects and other important criteria were accomplished through the formation of plaques of nucleated polypropylene thermoplastic resin. These plaques were formed through the process outlined above with the specific compositions listed above with a let-down of the nucleator salt as noted in Experimental Table 1, below. The resultant plaques were then tested for peak crystallization temperatures (by
  • Crystallization is important in order to determine the time needed to form a solid article from the molten polyolefin composition.
  • a polyolefin such as polypropylene has a crystallization temperature of about 105-110°C at a cooling rate of 20°C/min.
  • the best nucleator compound added will invariably also provide the highest crystallization temperature for the final polyolefin product.
  • the nucleation composition efficacy was evaluated by using a modified differential scanning procedure based upon the test protocol ASTM D3417-99 wherein the heating and cooling rates utilized have been altered to 20°C/minute each.
  • T c polymer peak crystallization temperature
  • Experimental Table 1 thus illustrates the challenge in obtaining optimum polymer Tc values with reasonable usage rates of the concentrate.
  • Examples 2 and 3 (1 and 1.5% HPN- 68 concentrates), for example, illustrate optimum nucleation performance, but the required usage rates in this scenario are not commercially viable. Beyond the 1.5% HPN-68 concentration, diminishing performance is observed. Therefore, it is seen that an HPN-68 concentrate having an HPN-68 concentration of 2% or greater suffers in performance in relation to a nucleated control. As the HPN-68 concentration moves higher, the performance penalty most likely results from inadequate dispersion of the site nucleator particles within the concentrate itself, combined with the corresponding decreasing usage level of the concentrate that inhibits adequate distributive mixing of the concentrate into the base polymer in which the let-down is made.
  • dispersion aid additives of calcium carbonate modified with stearates (SUPERCOAT®, reported to be a surface-modified, beneficiated, wet ground marble containing - 1-2% of a stearic acid, from Imerys, and having a mean particle size of 1.1 microns prior to surface modification) was added to concentrates of 20 MFR impact copolymer propylene (as for the initial concentrates above) and the same nucleator salt from the Example above. The amount of the dispersion aid additive was modified for different concentrates but the amount of nucleator salt was kept static for each example.
  • SUPERCOAT® calcium carbonate modified with stearates
  • plaque formulations are, of course, merely preferred embodiments of the inventive article and method and are not intended to limit the scope of this invention.
  • results for these dispersion aid additive-containing concentrates were as follows (with the same control nucleated resin present as in the first Experimental table, above):
  • the CaCO 3 was found to have a positive influence on HPN-68's capacity to nucleate when formulated together and within a concentrate. Optimum benefits appeared to be achieved at a 50% loading of CaCO 3 in the concentrate, thereby producing a final loading of 1% CaCO 3 in the final part (test specimen) under these typical let-down conditions. No benefits in nucleation were realized until the CaCO 3 reached - 25% in the concentrate (or -0.5%) in the final test specimen; such as in Example 5 of Experimental Table 2). Taking the optimized formulation containing 50% CaCO 3 and 5% HPN-68, further evaluations were performed at differing concentrate usage rates and subsequently differing final concentrations of HPN-68 to insure robust performance of the inventive compound.
  • the performance of the concentrate was compared to an HPN-68 nucleated control that had been previously melt compounded with the final target concentrations of HPN-68.
  • the concentrate carrier resin was a 12 MFR polypropylene homopolymer.
  • the concentrate was let-down into a non-nucleated, previously compounded 12 MFR polypropylene homopolymer.
  • the nucleated controls (Examples 1, 3, 5, and 7) were made from the same 12 MFR polypropylene homopolymer that had been previously compounded with the final target concentrations of HPN-68 (as above in the previous Experimental Tables).
  • thermoplastic nucleators aluminum para-tertiary butyl benzoic acid (Al-p-TBBA), and sodium 2,2'-methylene bis (4,6-di-t- butylphenyl) phosphate (NA-11, from Asahi Denka)].
  • talc SUZORITE® BT-2207 (reported to have a median particle size of 7 microns, from Zemex) was also evaluated as a substitution for CaC0 3 to determine if any synergistic effects could be identified with this commonly used polyolefin filler as well.
  • the concentrate carrier resin was a 20 MFR polypropylene impact copolymer.
  • the concentrates were let-down into a 12 MFR non-nucleated polypropylene homopolymer.
  • the nucleated controls (Examples 1, 5, and 9) were made from the same 12 MFR polypropylene homopolymer that had been previously melt compounded with 1000 ppm of the subject nucleator.
  • the inventive CaCO 3 concentrate formulation did not appear to offer any nucleation benefits to Al-p-TBBA or NA-11.
  • the effects of CaCO actually appeared to be slightly harmful in these situations.
  • Talc appeared to offer neutral results with Al-p-TBBA and deleterious results with NA-11 and HPN-68.
  • the inclusion of the above-noted preferred calcium carbonate dispersion aid additives within concentrates with the preferred class of bicyclic dicarboxylate salt nucleators provided surprisingly effective results as compared with concentrates of other nucleating agents.
  • CaCO 3 and stearic acid maybe imparting, a series of experiments was performed with a similar particle size CaCO 3 containing no stearic acid coating.
  • the brand of CaCO 3 used here was Sigma- Aldrich 310034, having an average particle size of 8.75 microns with no presence of stearic acid.
  • a comparative concentrate formulation was prepared containing 1% stearic acid with no CaCO 3.
  • the stearic acid brand used here was Sigma-Aldrich 17,536- 6.
  • the concentrate carrier resin was a 20 MFR polypropylene impact copolymer. The concentrates were let-down into a 12 MFR polypropylene homopolymer.
  • a nucleated control made from the same 12 MFR polypropylene homopolymer that had been previously melt compounded with 0.1 % HPN-68 was provided for comparison.
  • a 12 MFR polypropylene homopolymer carrier resin was used in the following Examples 3 and 4; in all other Examples the concentrate carrier resin was a 20 MFR polypropylene impact copolymer. All concentrates were let-down into a 12 MFR non- nucleated polypropylene homopolymer. And again, as in earlier tables, a nucleated confrol (Example 1) made from the same 12 MFR polypropylene homopolymer that had been previously melt compounded with 0.1% HPN-68 was provided for comparison.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des concentrés (appelés mélanges mères) de certains additifs nucléants thermoplastiques de sels de dicarboxylate bicycliques, ce qui permet de faciliter leur utilisation dans des procédés de fabrication thermoplastiques classiques. Lesdits additifs nucléants ont été conçus pour conférer des températures de cristallisation à pic élevé à des thermoplastiques (tels que le polypropylène), cependant, bien que combiné sous forme de mélange mère, la propriété de nucléation a été sacrifiée à cause de problèmes non pris en compte associés aux concentrés contenant des polymères (par exemple des boulettes) desdits additifs. Les améliorations dans la fabrication du mélange-mère desdits agents de nucléation thermoplastiques de sels de dicarboxylate bicycliques ont été apportées au niveau nécessaire permettant une utilisation concentrée présentant des effets de nucléation efficaces et concomitants au même niveau (sans excès) d'utilisation dudit agent de nucléation ajouté sous forme de poudre. L'invention concerne également des composition additives thermoplastiques et des procédés de production de produits thermoplastiques comprenant lesdits concentrés additifs d'agents de nucléation.
PCT/US2004/028437 2003-11-07 2004-09-01 Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques WO2005047383A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04782852A EP1680464A1 (fr) 2003-11-07 2004-09-01 Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/703,855 US7078450B2 (en) 2003-11-07 2003-11-07 Concentrates of saturated bicyclic dicarboxylate salts to facilitate use thereof as polymer nucleation additives
US10/704,391 US6995202B2 (en) 2003-11-07 2003-11-07 Methods of nucleating thermoplastics using concentrates of saturated bicyclic dicarboxylate salts
US10/704,391 2003-11-07
US10/703,855 2003-11-07

Publications (1)

Publication Number Publication Date
WO2005047383A1 true WO2005047383A1 (fr) 2005-05-26

Family

ID=34595357

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/028437 WO2005047383A1 (fr) 2003-11-07 2004-09-01 Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques

Country Status (2)

Country Link
EP (1) EP1680464A1 (fr)
WO (1) WO2005047383A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007033297A1 (fr) * 2005-09-16 2007-03-22 Milliken & Company Compositions polymères comprenant des agents de nucléation ou de clarification
WO2008064957A1 (fr) * 2006-12-01 2008-06-05 Basell Poliolefine Italia S.R.L. Procédé permettant de préparer des compositions de polybutène présentant une température de cristallisation plus élevée
WO2008073401A1 (fr) * 2006-12-11 2008-06-19 Milliken & Company Compositions d'additif de polymère et procédés associés
EP2380926A1 (fr) * 2010-04-26 2011-10-26 Borealis AG Mélange maître pour améliorer la rigidité et la transparence d'un copolymère de propylène aléatoire
WO2014099350A1 (fr) * 2012-12-21 2014-06-26 Dow Global Technologies Llc Tubes à structure libre à base de hdpe présentant une longueur de fibre excédentaire améliorée pour câbles à fibre optique
US9688689B2 (en) 2014-05-13 2017-06-27 Novartis Ag Compounds and compositions for inducing chondrogenesis
CN111286128A (zh) * 2020-03-26 2020-06-16 青岛科技大学 一种快速成型的聚丁烯树脂及其制备方法
CN113444343A (zh) * 2021-07-15 2021-09-28 中化石化销售有限公司 超支化微晶成核剂的制备方法及聚烯烃树脂的制备方法
CN113549246A (zh) * 2021-07-15 2021-10-26 中化石化销售有限公司 超支化微晶成核剂组合物及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465551B1 (en) * 2001-03-24 2002-10-15 Milliken & Company Bicyclo[2.2.1]heptane dicarboxylate salts as polyolefin nucleators

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6465551B1 (en) * 2001-03-24 2002-10-15 Milliken & Company Bicyclo[2.2.1]heptane dicarboxylate salts as polyolefin nucleators

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7786203B2 (en) 2005-09-16 2010-08-31 Milliken & Company Polymer compositions comprising nucleating or clarifying agents and articles made using such compositions
WO2007033297A1 (fr) * 2005-09-16 2007-03-22 Milliken & Company Compositions polymères comprenant des agents de nucléation ou de clarification
WO2008064957A1 (fr) * 2006-12-01 2008-06-05 Basell Poliolefine Italia S.R.L. Procédé permettant de préparer des compositions de polybutène présentant une température de cristallisation plus élevée
WO2008073401A1 (fr) * 2006-12-11 2008-06-19 Milliken & Company Compositions d'additif de polymère et procédés associés
EP2380926A1 (fr) * 2010-04-26 2011-10-26 Borealis AG Mélange maître pour améliorer la rigidité et la transparence d'un copolymère de propylène aléatoire
US9969859B2 (en) 2012-12-21 2018-05-15 Dow Global Technology Llc HDPE-based buffer tubes with improved excess fiber length in fiber optic cables
WO2014099350A1 (fr) * 2012-12-21 2014-06-26 Dow Global Technologies Llc Tubes à structure libre à base de hdpe présentant une longueur de fibre excédentaire améliorée pour câbles à fibre optique
US10188638B2 (en) 2014-05-13 2019-01-29 Novartis Ag Compounds and compositions for inducing chondrogenesis
US9688689B2 (en) 2014-05-13 2017-06-27 Novartis Ag Compounds and compositions for inducing chondrogenesis
US10383863B2 (en) 2014-05-13 2019-08-20 Novartis Ag Compounds and compositions for inducing chondrogenesis
US10660881B2 (en) 2014-05-13 2020-05-26 Novartis Ag Compounds and compositions for inducing chondrogenesis
US11510912B2 (en) 2014-05-13 2022-11-29 Novartis Ag Compounds and compositions for inducing chondrogenesis
CN111286128A (zh) * 2020-03-26 2020-06-16 青岛科技大学 一种快速成型的聚丁烯树脂及其制备方法
CN113444343A (zh) * 2021-07-15 2021-09-28 中化石化销售有限公司 超支化微晶成核剂的制备方法及聚烯烃树脂的制备方法
CN113549246A (zh) * 2021-07-15 2021-10-26 中化石化销售有限公司 超支化微晶成核剂组合物及应用
CN113549246B (zh) * 2021-07-15 2023-09-19 中化石化销售有限公司 超支化微晶成核剂组合物及应用

Also Published As

Publication number Publication date
EP1680464A1 (fr) 2006-07-19

Similar Documents

Publication Publication Date Title
US6995202B2 (en) Methods of nucleating thermoplastics using concentrates of saturated bicyclic dicarboxylate salts
EP1373396B1 (fr) Articles thermoplastiques fortement nuclees
US7332536B2 (en) Metal salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics
US6562890B2 (en) Disodium hexahydrophthalate salt compositions and nucleated polymers comprising such compositions
US7078450B2 (en) Concentrates of saturated bicyclic dicarboxylate salts to facilitate use thereof as polymer nucleation additives
US6946507B2 (en) Nucleating additive formulations of bicyclo[2.2.1]heptane dicarboxylate salts
US6936650B2 (en) Nucleating additive formulations of bicyclo[2.2.1]heptane dicarboxylate salts
WO2005047383A1 (fr) Concentres de sels de dicarboxylate bicycliques satures utilises en tant qu'additifs de nucleation polymeres et procedes de nucleation de produits thermoplastiques
EP1668071B1 (fr) Formulations ameliorees d'additifs de nucleation a base de sels de dicarboxylate de bicyclo 2.2.1 heptane
US6599968B2 (en) Thermoplastic nucleating compounds

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480037146.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2004782852

Country of ref document: EP

Ref document number: 2542/DELNP/2006

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 2004782852

Country of ref document: EP