WO2005017018A1 - Thermoplastiques et polypropylenes presentant une excellente resistance a la pression hydrostatique a long terme, destines a des applications a haute pression - Google Patents

Thermoplastiques et polypropylenes presentant une excellente resistance a la pression hydrostatique a long terme, destines a des applications a haute pression Download PDF

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Publication number
WO2005017018A1
WO2005017018A1 PCT/US2004/021919 US2004021919W WO2005017018A1 WO 2005017018 A1 WO2005017018 A1 WO 2005017018A1 US 2004021919 W US2004021919 W US 2004021919W WO 2005017018 A1 WO2005017018 A1 WO 2005017018A1
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WIPO (PCT)
Prior art keywords
geminal
hydroxy
constituents
article
group
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Application number
PCT/US2004/021919
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English (en)
Inventor
Stephane Berghmans
Mark Boelens
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 US10/639,550 external-priority patent/US20050038155A1/en
Priority claimed from US10/639,665 external-priority patent/US20050038156A1/en
Application filed by Milliken & Company filed Critical Milliken & Company
Publication of WO2005017018A1 publication Critical patent/WO2005017018A1/fr

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    • 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
    • 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

Definitions

  • the present invention generally relates to novel thermoplastics and pipes made therefrom which can withstand extreme surface and/or internally generated pressures that make them excellent candidates for high-pressure uses, such as, as one non-limiting example, within underground liquid and gas transport systems.
  • Such high-pressure articles are improvements over standard metal (i.e., steel, copper, lead, and the like), concrete, ceramic, and the like, articles due to toxicity issues (such as with lead pipes), raw material costs (such as with copper), construction costs, shipping costs, implementation costs (particularly underground), flexibility (and thus modulus strength allowances) to compensate for underground movements (i.e., earthquakes and tremors), non-rusting characteristics, reduced crack propagation possibilities, and ease in manufacture.
  • Such thermoplastics exhibit excellent long-term hydrostatic strength characteristics that permit potential long-term reliable usage in underground conditions and are preferably made from resins that include nucleating agents that provide such needed properties therein. Background of the Invention Underground transport of liquids and gases has been utilized for many years.
  • Such underground transport has proven to be the most efficient and safest manner in which to transport potentially explosive, flammable, and/or toxic liquids (such as crude oil, for example) and gases (such as methane and propane, as examples) long distances.
  • toxic liquids such as crude oil, for example
  • gases such as methane and propane, as examples
  • the principal method followed to provide such long distance underground transport has been through metal tubes and pipes.
  • metals such as steel, copper, lead, and the like
  • thermoplastic pipe materials exhibiting sufficiently high hydrostatic strength over a long period of time (for example, 50 years or more).
  • the thermoplastic materials currently provided today lack such a long-term high pressure strength characteristic, at least to the extent that reliability for long periods of time is not in doubt.
  • Another object of this invention is to provide a viable alternative to high-pressure questionable metal materials.
  • Another object of this invention is to provide a suitable and reliable thermoplastic material for the replacement of the materials currently utilized for underground liquid- and gas-transport pipes.
  • Yet another object of this invention is to provide a simple manner of providing a thermoplastic (polyolefin, such as polypropylene, for example) exhibiting sufficiently high reliable long-term hydrostatic strength for such high- pressure applications (pipes, as one non-limiting example).
  • this invention encompasses a nucleated thermoplastic formulation wherein said formulation exhibits a lower prediction limit ratio at least 3.0, preferably at least 3.2, more preferably at least 3.5, and most preferably at least 3.1, in comparison with a nonnucleated thermoplastic formulation of the same base resin, said lower prediction limit indicating long-term hydrostatic strength and performed in accordance with a full notch creep test for suitable solid plaque articles having dimensions of 100 mm by 6 mm by 6 mm and having a 1 mm notch cut into the middle portion therein.
  • a high-pressure article preferably, though not necessarily, a pipe
  • a nucleated thermoplastic formulation as above is also encompassed within this invention.
  • such a nucleated thermoplastic formulation comprising at least one bicyclic nucleating agent or at least one cyclic dicarboxylate nucleating agent is also encompassed, as well as the method of forming such a formulation comprising the steps of introducing a bicyclic or cyclic dicarboxylate nucleating agent into a molten thermoplastic composition and permitting such a nucleated formulation to cool into a nucleated thermoplastic formulation and/or article.
  • Thermoplastic formulations exhibiting such long-term hydrostatic strength, as well as certain pipes, either or both comprising specific nucleating agents, as noted below, are also encompassed within this invention.
  • thermoplastic is intended to encompass the well known polymeric compositions of any synthetic polymeric material that exhibits a modification in physical state from solid to liquid upon exposure to sufficiently high temperatures.
  • polyolefms i.e., polypropylene, polyethylene, and the like
  • polyester i.e., polyethylene terephthalate, and the like
  • polyamides i.e., nylon- 1J, nylon-1,2, nylon-6 or nylon-6,6
  • polyvinyl halides i.e., polyvinyl chloride and polyvinvyl difluoride, as merely examples.
  • Preferred within this invention are polyolefms, and most preferred is polypropylene.
  • Such materials are generally petroleum byproducts and are readily available worldwide. These materials are produced through the polymerization of similar or different monomers in a number of well-established commercial processes to yield, generally, pelletized resins. There are readily processed by melt extrusion of the polymerized materials in pellet form into the desired shape or configuration.
  • such materials Upon solidification through cooling, such materials exhibit extremely high pressure resistance, particularly upon introduction of nucleating agents, such as, as previously utilized in widespread applications, substituted or unsubstituted dibenzylidene sorbitols, available from Milliken & Company under the tradename Millad®, particularly l,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS), available from Milliken Chemical under the trade name Millad® 3988, and/or certain sodium organic salts, available from Asahi Denka Kogyo K.K.
  • nucleating agents such as, as previously utilized in widespread applications, substituted or unsubstituted dibenzylidene sorbitols, available from Milliken & Company under the tradename Millad®, particularly l,3-O-2,4-bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS), available from Milliken Chemical
  • nucleating agents are either mixed and provided within the pelletized polymers, or admixed within the melted polymer composition prior to extrusion. These compounds provide strength enhancements and accelerate thermoplastic production by producing crystalline networks within the final thermoplastic product upon cooling at relatively high temperatures.
  • high-pressure article is intended to encompass thermoplastic articles of any size or shape that can withstand internally and/or externally applied pressures of at least 8 bars. Such articles may be utilized for myriad applications, most notably as pipes for liquid and/or gas transport, either aboveground or underground. Other applications for such articles include, without limitation, liquid and/or gas storage devices (pressurized containers, for instance), plastic tanks (for fertilizers, alcoholic beverages, and the like, that may exhibit gas and/or vapor expansion properties during storage and/or transport), commode materials (particularly such materials as are prone to high air pressures in flushing systems), and the like.
  • the wall thicknesses required to provide the desired high pressure characteristics are extremely high for standard thermoplastics (such as those including the nucleators noted above). Although such standard thermoplastic materials provide certain pressure resistances, in general the wall thickness required to withstand pressures of about 80 bars requires a standard diameter to wall thickness ratio of at most 11 :1, although such a ratio is not intended to limit the breadth of this invention, only as a guide to standard characteristics of certain thermoplastics in terms of pressure properties.
  • the wall thickness of the pipe must be at least about 21 millimeters, or about 0.85 inches) to withstand such high pressures.
  • Such thick walls may provide pressure resistance as well as resistance to crack propagation in certain situations; however, there is a strong desire to provide surface pressure resistance as well, not to mention the ability to reduce the amount of thermoplastic material required to provide such beneficial properties.
  • burst pressure resistance has been provided in the past through the introduction of reinforcement materials within the target pipes themselves (such as metal, textile, and other like materials embedded within the pipes). However, such materials accord improvements in terms of burst pressure, but do not accord the same improvements in surface pressures.
  • the nucleated thermoplastics noted within this invention have been found to provide an unforeseen improvement in such a pressure resistance level such that, as one example, the amount of thermoplastic necessary to meet a required gauge level can be reduced in comparison with the amounts required of prior nucleated thermoplastics.
  • the thermoplastic is preferably nucleated and most preferably comprises at least one nucleating agent compound selected from the group consisting of compounds conforming with either of formulae (I) or (II) (I)
  • Mi and M 2 are the same or different or are combined to form a single moiety and are selected from at least one metal cation (such as, without limitation, sodium, potassium, calcium, strontium, lithium, and monobasic aluminum), and wherein Ri, R 2 , R , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and Rio are either the same or different and are individually selected from the group consisting of hydrogen, C ⁇ -C 9 alkyl [wherein any two vicinal (neighboring) or geminal (same carbon) alkyl groups may be combined to form a carbocyclic ring of up to six carbon atoms], hydroxy, Cj-C alkoxy, C ⁇ -C 9 alkyleneoxy, amine, and C ⁇ -C 9 alkylamine, halogens (fluorine, chlorine, bromine, and iodine), and phenyl, wherein geminal constituents may be the same except that such geminal constituents cannot simultaneously be hydroxy;
  • the stereochemistry at the metal carboxylates may be cis or trans, although cis is preferred.
  • Calcium ct-s-hexahydrophthalate and disodium ct-s-hexahydrophthalate are preferred embodiments, although other metal ions, half esters, and pendant group substitutions as in the formula above, should provide similarly effective results.
  • the stereochemistry at the R' and R" groups may be cis-exo, cis-endo, or trans, although cis-endo is preferred.
  • Preferred embodiments of such a compound are disodium or calcium bicyclo[2.2J]heptane- c ⁇ -e « o-2,3-dicarboxylate, although other metal ions, half esters, and pendatn group substitutions as in the formula above, should provide similarly effective results.
  • inventive pipes when subjected to external shear forces, for example earth tremors, and the like.
  • Such flexibility permits the pipes to exhibit some movement in relation to the shear forces generated by such external occurrences.
  • metal pipes suffered from the lack of flexibility in that the application of such external shear forces would result in the burst of certain pipes due to such external forces exceeding the shear force threshold possessed by the metal materials.
  • Such flexibility is most suitably measured in terms of tear resistance to the overall pipe article.
  • metal pipes exhibit at most a tear resistance of about 6% (copper exhibits the highest such tear resistance), which is extremely low when the potential for very strong shear forces underground are significant (particularly in certain parts of the world prone to earth tremors, earthquakes, and the like).
  • Thermoplastics provide initial tear resistance measurements in excess of at least 20%, with a potential high measurement of more than about 100%, particularly upon incorporation of the sandwiched textile reinforcement material as discussed above.
  • the inventive pipes should be able to withstand enormous shear forces, at least better than metal pipes, due to their exhibited tear resistance and thus flexibility characteristics.
  • the thermoplastic material layer or layers may comprise any number of additives for standard purposes, such as antimicrobial agents, colorants, antistatic compounds, and the like.
  • antimicrobial agents would potentially protect the inner lining from colonization of unwanted and potentially dangerous bacteria (which could potentially create greater pressure within the pipes if a proper nutrition source is present).
  • an antimicrobial agent would be inorganic in nature and relatively easy to introduce within the thermoplastic compositions within the pipe.
  • silver-based ion-exchange compounds such as ALPHASAN®, available from Milliken & Company, and other types, such as silver zeolites, and the like
  • Colorants may be utilized to easily distinguish the thermoplastic layers for identification purposes.
  • any pigment, polymeric colorant, dye, or dyestuff which is normally utilized for such a purpose may be utilized in this respect for this invention.
  • Antistatic compounds such as quaternary ammonium compounds, and the like, permit static charge dissipation within the desired thermoplastic materials in order to reduce the chances of instantaneous spark production which could theoretically ignite certain transported gases and/or liquids. Although the chances of such spark ignition are extremely low, such an additive may be necessary to aid in this respect.
  • textile reinforcements may also be introduced between layers of thermoplastic material to add strength in terms of burst pressures, if desired. Although only one specific layer of nucleated thermoplastic material is required, it is to be understood that more than one such layer is acceptable within this invention.
  • Such additional layers may be of any type (and not necessarily thermoplastic and/or thermoset, or even nucleated thermoplastic, if desired), including, without limitation, metal, ceramic, glass- filled plastic, rubber, and the like.
  • thermoplastic and/or thermoset or even nucleated thermoplastic, if desired
  • metal, ceramic, glass- filled plastic, rubber, and the like including, without limitation, metal, ceramic, glass- filled plastic, rubber, and the like.
  • Thermoplastic compositions were produced comprising the additives from the Examples above and sample random polyproylene (with some ethylene content) copolymer (RCP) resin plaques, produced dry blended in a Welex mixer at ⁇ 2000 rpm, extruded through a single screw extruder at 205-220°C, and pelletized. Accordingly, one kilogram batches of target polypropylene were produced in accordance with the following table:
  • Polypropylene random copolymer (Repsol Isplen PR230®) 1000 g
  • Irganox® 1010 Primary Antioxidant (from Ciba) 500 ppm Irgafos® 168, Secondary Antioxidant (from Ciba) 1000 ppm
  • the base RCP and all additives were weighed and then blended in a Welex mixer for 1 minute at about 1600 rpm. All samples were then melt compounded on a Killion single screw extruder at a ramped temperature from about 205° to 220°C through four heating zones. The melt temperature upon exit of the extruder die was about 220°C. The screw had a diameter of 2.54 cm and a length/diameter ratio of 24:1. Upon melting the molten polymer was filtered through a 60 mesh (250 micron) screen. Plaques of the target polypropylene were then made through compression molding of the pellets in a heated press. The plaques had dimensions of about 100 mm X 6 mm X 6 mm.
  • 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.
  • the Long-Term Hydrostatic Strength (LTHS) is measured by exposing pipes to different stresses at different temperatures and recording the time elapsed before the pipe loses its dimensional stability and thus fails (via cracking, wall collapse, or the like).
  • the individual bars were then subjected to constant stresses (to simulate the effect of internal pressures) through pulling apart of the long ends of the bar in a water bath (including 2% of a surfactant, in this situation Arkopal® N100) and at desired temperatures (in this situation 80°C).
  • the measure of creep of the notch e.g., an increase in the size and shape thereof
  • This test is not intended to be a replacement for LTHS if such is desired (for measurements of months, for example) and is only utilized as a predictability screen for LTHS for excessive amounts of time (50 years, for example).
  • different stresses were applied to the sample bars and the time to breakage was recorded for each.
  • a regression according to ISO/DIS 9080 was then followed to calculate the predicted LTHS for each bar up to 50 years time. The stresses were measured as follows:
  • K 10 8.39 K 11 7.55 K 33 6.01 K 48 5.2 K 130 4.12 K 450 3.28 K 1293 2.64 K 2650 2.24 L 7 7.55 L 8 7.48 L 21 6.29 L 48 5.04 L 79 4.42 L 136 3.77 L 142 3.70 L 302 3.15 L 689 2.64 L 745 2.57 L 1240 2.15 L 1496 2.04 M 15 7.46 M 22 6.34 M 85 4.92 M 114 4.42 M 145 3.80 M 245 3J4 M 653 2.51 M 769 2.46 M 1287 2.04 M 1345 2.01
  • the lower prediction limit for LTHS (the stress a material can withstand under the current test conditions after 50 years of same pressure exposure and is a measure of the pressure resistance of the material as if it were processed into a pipe article) in accordance with the Standard Extrapolation Method, based on ISO/DIS 9080 (version 1999).
  • the lower prediction limit basically is an estimation of the lowest pressure that will rupture the sample thermoplastic after 50 years of use.
  • the ratio comparison of the LPL measurements thereof are provided as well versus the nonucleated sample as an indication of the improvement in ability withstand internal and external pressures for a long period of time (again, extrapolated to 50 years), and thus an indication of the reliability of the sample thermoplastics in terms of long-term hydrostatic strength.
  • the LPL shows an increase of at least 1.08 (at lower levels) and can exceed 2.75 times, preferably at least 3 times, the LPL of the original non-nucleated resin, and, alternatively at least to a level of 0.6 MPa pressure resistance over such a theoretical long period of time, a level heretofore unattained for nucleated resins.
  • inventive nucleated resins thus provide at least effective ability to withstand long-term hydrostatic pressures, if not unexpectedly good and reliable thermoplastics for long-term pressure-resistant pipe (and similar object) end-uses.

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

Abstract

L'invention concerne de nouveaux thermoplastiques, et des tuyaux fabriqués à partir desdits thermoplastiques et pouvant supporter des pressions externes et/ou internes extrêmes qui en font d'excellents articles utilisables dans des systèmes souterrains de transport de liquides ou de gaz. Ces tuyaux constituent des améliorations par rapport aux tuyaux classiques en métal (acier, cuivre, plomb et analogues), en béton, céramique et analogues, du fait des problèmes que ces derniers posent en termes de toxicité (tuyaux en plomb), de coût des matières premières (tuyaux en cuivre), de coût de construction, d'expédition, de mise en oeuvre (notamment pour une implantation souterraine), de souplesse (et donc de marges de tolérance du module de résistance) de correction des mouvements souterrains (tremblements de terre et secousses sismiques); lesdits tuyaux présentant des caractéristiques d'inoxydation, une sensibilité à la propagation des fissures réduite, et la facilité de fabrication. Les thermoplastiques de l'invention présentent d'excellentes caractéristiques de résistance à la pression hydrostatique à long terme, qui assurent une utilisation potentielle fiable à long terme dans des conditions d'emploi souterrain. Ils sont fabriqués à partir de résines comprenant des agents nucléants qui leur confèrent lesdites propriétés désirées.
PCT/US2004/021919 2003-08-12 2004-07-09 Thermoplastiques et polypropylenes presentant une excellente resistance a la pression hydrostatique a long terme, destines a des applications a haute pression WO2005017018A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/639,550 US20050038155A1 (en) 2003-08-12 2003-08-12 Thermoplastics exhibiting excellent long-term hydrostatic strength for high-pressure applications
US10/639,550 2003-08-12
US10/639,665 US20050038156A1 (en) 2003-08-12 2003-08-12 Polypropylenes exhibiting excellent long-term hydrostatic strength for high-pressure applications
US10/639,665 2003-08-12

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WO2005017018A1 true WO2005017018A1 (fr) 2005-02-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103483688A (zh) * 2013-10-15 2014-01-01 重庆顾地塑胶电器有限公司 抗冲击和抗拉伸的β-晶型聚丙烯复合材料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981636A (en) * 1996-12-27 1999-11-09 3M Innovative Properties Company Modifying agents for polyolefins
US6465551B1 (en) * 2001-03-24 2002-10-15 Milliken & Company Bicyclo[2.2.1]heptane dicarboxylate salts as polyolefin nucleators
US6599971B2 (en) * 2001-03-29 2003-07-29 Milliken & Company Metals salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981636A (en) * 1996-12-27 1999-11-09 3M Innovative Properties Company Modifying agents for polyolefins
US6465551B1 (en) * 2001-03-24 2002-10-15 Milliken & Company Bicyclo[2.2.1]heptane dicarboxylate salts as polyolefin nucleators
US6599971B2 (en) * 2001-03-29 2003-07-29 Milliken & Company Metals salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103483688A (zh) * 2013-10-15 2014-01-01 重庆顾地塑胶电器有限公司 抗冲击和抗拉伸的β-晶型聚丙烯复合材料及其制备方法和应用

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