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WO1996008532A1 - Stabilisation des polymeres de polyethylene - Google Patents

Stabilisation des polymeres de polyethylene Download PDF

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Publication number
WO1996008532A1
WO1996008532A1 PCT/US1995/011447 US9511447W WO9608532A1 WO 1996008532 A1 WO1996008532 A1 WO 1996008532A1 US 9511447 W US9511447 W US 9511447W WO 9608532 A1 WO9608532 A1 WO 9608532A1
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WO
WIPO (PCT)
Prior art keywords
diphenylamine
composition
stabilizing
polyethylene
recited
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1995/011447
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English (en)
Inventor
Robert Allen Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uniroyal Chemical Co Inc
Original Assignee
Uniroyal Chemical Co Inc
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Filing date
Publication date
Application filed by Uniroyal Chemical Co Inc filed Critical Uniroyal Chemical Co Inc
Publication of WO1996008532A1 publication Critical patent/WO1996008532A1/fr
Anticipated expiration legal-status Critical
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • This invention relates to a method for stabilizing a polyethylene composition against degradation, which comprises incorporating into the polyethylene composition, a stabilizing composition comprising a pentaerythritol diphosphite, and at least one diphenylamine derivative and/or at least one sterically hindered phenol.
  • this invention relates to a method for stabilizing linear low density polyethylene (LLDPE) against degradation, which comprises incorporating into the linear low density polyethylene, a stabilizing composition comprising a pentaerythritol diphosphite, and at least one diphenylamine derivative and/or at least one sterically hindered phenol.
  • LLDPE linear low density polyethylene
  • This invention also relates to polyethylene compositions stabilized against degradation.
  • a long-standing problem of plastic goods manufacturers is stabilizing polyethylene resins during high temperature, high shear blending and extrusion processes which are common in plastic goods manufacturing. It has been found that resins that show excellent long-term thermal heat stability characteristics may not be sufficiently protected against the type of degradation which occurs in an extruder during long residence times.
  • LLDPE linear low density polyethylene
  • various antioxidants, stabilizers, and additives are added to the raw polymer to prevent oxidation, discoloration, and thermal degradation during melt processing.
  • compositions of certain antioxidants have been described as useful for the stabilization of polyethylene polymers.
  • U.S. Patent No. 4,187,212 describes the use of a stabilization system consisting of triarylphosphite and a phenolic antioxidant, for stabilizing polyolefins.
  • U.S. Patent No. 4,837,259 describes the use of an antioxidant composition consisting of an amine and a phenol, to stabilize polypropylene.
  • U.S. Patent No. 5,096,590 describes the use of a composition containing hindered amines and phenolic stabilizers, for stabilizing polyolefins.
  • 2,252,324A describes a composition containing a phenolic or amine antioxidant, a metal deactivator, and a neutralizer and/or a phosphorous-containing antioxidant, for stabilizing polyolefins.
  • U.S. Patent No. 5,155,153 describes a stabilizing composition for thermoplastic organic polymers consisting of a hindered phenol, a triaryl phosphite, and a dialkylthiodipropionate.
  • U.S. Patent 5,526,333 describes a stabilizing composition consisting of 3-component mixture of a diphenylamine, a hindered phenol, and a pentaerythritol diphosphite, useful as an additive for polyether polyols.
  • This invention relates to a method for stabilizing a polyethylene composition against degradation, which comprises incorporating into the polyethylene composition, an effective stabilizing amount of a stabilizing composition which comprises:
  • the stabilizing composition in the method of this invention comprises: a) a pentaerythritol diphosphite; b) at least one diphenylamine selected from the group consisting of alkyl-substituted diphenylamine and aralkyl-substituted diphenylamine; and c) at least one sterically hindered phenol.
  • the method of the present invention protects the polyethylene composition against the adverse effects of actinic, oxidative and thermal degradation by substantially reducing the discoloration and other degradative effects which result from the processing of the polyethylene composition.
  • polyethylene composition means a composition which comprises one or more polyethylene homopolyrners, polyethylene copoly ers, or blends of homopolyrners and copolymers.
  • Preferred polyethylene compositions comprise LLDPE.
  • This invention also relates to a polyethylene composition stabilized against degradation, comprising:
  • a pentaerythritol diphosphite (i) a pentaerythritol diphosphite; and (ii) an antioxidant compound selected from the group consisting of :
  • At least one diphenylamine selected from the group consisting of alkyl-substituted diphenylamine and aralkyl-substituted diphenylamine;
  • the polyethylene composition comprises an effective stabilizing amount of a stabilizing composition comprising: a) a pentaerythritol diphosphite; b) at least one diphenylamine selected from the group consisting of alkyl-substituted diphenylamine and aralkyl-substituted diphenylamine; and c) at least one sterically hindered phenol.
  • a stabilizing composition comprising: a) a pentaerythritol diphosphite; b) at least one diphenylamine selected from the group consisting of alkyl-substituted diphenylamine and aralkyl-substituted diphenylamine; and c) at least one sterically hindered phenol.
  • the term "effective stabilizing amount” is intended to signify that amount of the stabilizing composition necessary to stabilize the polyethylene composition for performance in actual use.
  • the effective stabilizing amount of the stabilizing composition will vary depending upon the polyethylene composition used, but, in general, will be within the range of about 0.01 to 5.0% by weight of the polyethylene composition, and, preferably, from about 0.05 to 0.5% by weight of the polyethylene composition.
  • this invention is directed to a method for stabilizing a linear low density polyethylene compostion against degradation which comprises incorporating into the LLDPE composition, an effective stabilizing amount of a stabilizing composition which comprises : (a) a pentaerythritol diphosphite; and (b) an antioxidant component selected from the group consisting of:
  • the improved stabilization is also evidenced by the melt viscosity data presented in Tables 1 and 2.
  • the melt viscosity data indicates the uniformity of the flow rate of the polymer and is indicative of uniformity of other properties, as will be described below.
  • the diphenylamines, hindered phenols and pentaerythritol diphosphites that are employed in the stabilizing composition of the method of this invention are individually well known compounds.
  • the pentaerythritol diphosphites that can be utilized in the stabilizing composition of this invention are preferably the sterically hindered bis(aryl)- pentaerythritol diphosphites, numerous examples of which are known in the art. See, e.g., U.S. Patents Nos.
  • aryl groups are substituted with alkyl groups from about 1 to about 20 carbon atoms are particularly preferred.
  • the aryl groups are preferably phenyl groups and contain branched alkyl groups in the 2 and 4 positions relative to one another on the phenyl ring.
  • An example of such a phosphite is distearyl pentaerythritol diphosphite.
  • An especially preferred pentaerythritol diphosphite for use in the instant invention is bis (2, 4-di-t- butylphenyDpentaerthrytol diphosphite (BPD) , which is available under the tradename Ultranox 626 (General Electric Specialty Chemicals) .
  • BPD is a high performance solid organophosphate antioxidant which is known for its stabilization of polyolefins, polyesters, styrenes, engineering thermoplastics, polyvinyl chlorides, elastomers and adhesives .
  • the pentaerythritol diphosphite component will generally be present in amounts from about 30 to about 70, preferably, from about 40 to about 60, and, most preferably, from about 45 to about 55, weight percent based on the entire weight of stabilizing composition. Pentaerythritol diphosphites are more effective for use in the antioxidant composition of this invention than other phosphites currently in use as additives in the manufacture of polymeric materials .
  • Examples of such other phosphites are tris (nonylphenyl) phosphite, phenyl diisodecyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tridecyl phosphite and triisooctyl phosphite.
  • diphenylamines useful in the composition of this invention have the formula
  • R 1 and R 4 are hydrogen, C 1 -C 4 alkyl or phenyl, preferably phenyl; and R 2 , R 3 , R 5 and R 6 are hydrogen or C 1 -C 4 alkyl, preferably methyl.
  • a preferable diphenylamime that can be employed in this compostion is 4, 4' -bis ( ⁇ ,of-dimethylbenzyl) -diphenylamine, also known as Naugard 445 * (Uniroyal Chemical Company, Inc.) .
  • the amount of diphenylamine in the stabilizing composition useful in this invention can vary, e.g., from about 10 to about 70, preferably from about 20 to about 60, and most preferably from about 20 to about 30, weight percent based on the entire weight of stabilizing composition.
  • Suitable hindered phenols that can be utilized in the stabilizing composition herein include 2,4-dimethyl- 6-octylphenol, 2, 6-di-t-butyl-4-methylphenol, 2,6-di-t- butyl-4-nonylphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,6- di-t-butyl-4-n-butylphenol, 2, 6-di-t-butyl-4-sec- butylphenol, 2, 2' -methylenebis (4-methyl-6-t-butylphenol) , 2,2' -methylenebis (4-ethyl-6-t-butylphenol) , 2,4-dimethyl- 6-t-butylphenol, 4-hydroxymethyl-2, 6-di-t-butylphenol, n- octadecyl- ⁇ (3, 5 di-t-butyl-4-hydroxyphenyl)propionate,
  • a preferred hindered phenol is octadecyl 3, 5-di-t-butyl-4-hydroxyhydrocinnamate, which is commercially available under the tradename Naugard 76 (Uniroyal Chemical Company, Inc.)
  • Other preferred hindered phenols include tetrakis [methylene-3- (3, 5-di-t- butyl-4-hydroxyphenyl)propionate] methane and 2,2'- oxamidobis (ethyl) -3 (3, 5-di-t-butyl-4- hydroxyphenyDpropionate, which are commercially available under the tradenames Naugard 10 and Naugard XL- 1 (both trademarks of the Uniroyal Chemical Company, Inc . )
  • the hindered phenol component of the stabilizing composition useful in the method of this invention can be present therein in widely varying amounts, e.g., from about 10 to about 70, preferably from about 20 to about
  • Linear low density polyethylene is a low density polyethylene produced by a low pressure process, by
  • the low density is due to reduced crystallinity resulting from the use of up to about 10% of a 1-alkene comonomer such as 1-butene.
  • the polymer contains short carbon chain side groups which reduce structural regularity and hence crystallization.
  • LLDPE is used in such applications as film, pipe, rotational molding, injection molding, and wire and cable resins.
  • finishing process the operations associated with conversion of the dry product from the reactor into a form suitable for final processing for customer use are termed the finishing process.
  • the finishing process may comprise stabilization, blending, extrusion, and pelletizing.
  • the stabilizing composition useful in the method of this invention is produced in powder form, and is added at the pre-compounding stage to powdered polyethylene which is then pelletized.
  • the stabilizing composition can be readily incorporated into the polyethylene composition by conventional techniques for incorporating such additives into polyolefin resins.
  • the components of the stabilizing composition can be introduced into the polyethylene composition as a premix, or the components can be maintained separately and added to the polyethylene composition simultaneously or sequentially, and then homogeneously distributed throughout the polyethylene composition by milling, extrusion blending, or some other mechanical working procedure.
  • additives can also be introduced into the polyethylene composition prior to, during and/or following addition of the stabilizing composition components.
  • additives include other stabilizers, colorants, reinforcements, fillers, antistatic agents, lubricants, plasticizers, and the like.
  • Each tested component of the stabilizing composition or each tested organic monophosphite compound was dry blended into powdered LLDPE (gas phase Unipol type Linear Low Density Polyethylene from Mobil Chemical Company) and stirred for sufficient time to ensure adequate dispersion of the additive and LLDPE. 500 ppm of zinc stearate, employed as an acid neutralizer, was then added to each mixture, to produce the test sample.
  • LLDPE gas phase Unipol type Linear Low Density Polyethylene from Mobil Chemical Company
  • test sample was then pelletized by extrusion on a 3/4 inch extruder.
  • the melt temperature and control zones on the extruder and die were adjusted to attain a melt temperature of 450°F.
  • Each pellet so formed was then rerun through the extruder five times to simulate multiple heat histories and promote degradation of the polymer.
  • measurement of melt viscosity measurements were taken only on the first, third, and fifth passes through the extruder.
  • the test samples having the best stabilization were affected the least; that is, the melt index values were consistant between the first, third, and fifth extrusions.
  • the data for Comparative Examples A-K are presented in Table 1.
  • two- or three- component compositions were evaluated for stabilization efficacy in LLDPE compositions.
  • the classes of compounds used were hindered phenols, aromatic amines, and organic phosphites.
  • the compounds used are commercially available and are known stabilizers for polyethylene polymers individually or in binary combinations.
  • the data shown in Table 2 indicate the surprising improvements in stabilization efficiency using the stabilizing compositions useful in the method of this invention. Samples were made and evaluated according to the procedures indicated above. A wide range of phenolic stabilizers were tested.
  • the amine that was used, Naugard 445 (trademark, Uniroyal Chemical Company, Inc.) , is 4,4' -bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine.
  • Naugard is a trademark of the Uniroyal Chemical Co.
  • Naugard 10 Tetrakis [methylene-3-(3,5-di-tert-butyl-4 hydroxyphenyl)propionate] methane
  • Naugard 445 4,4' Bis ⁇ , ⁇ -dimethylbenzyl) diphenylamine
  • Naugard XL-1 2,2' Oxamidobis [ethyl-3(3,5-di-tert*butyl-4-hydroxyphenyl) propionate]
  • Naugard 524 Tris (2,4-di-tert-butylphenyl) phosphite
  • Naugard P Tris (monononylphenyl) phosphite
  • Ultranox 626 Bis (2,4-di-tert-butyl) pe ⁇ taerythriol diphosphite TABLE 2 EXAMPLES 1-21: TWO AND THREE COMPONENT COMPOSITIONS
  • N-XL-1 N-P 500 500 9.0 1.22 1.21 1.16

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Procédé de stabilisation d'une composition polyéthylènique, telle qu'un polyéthylène linéaire à faible densité, contre la dégradation, par incorporation dans la composition polyéthylènique d'une quantité efficace d'une composition de stabilisation renfermant: (a) un diphosphite de pentaérythritol; et (b) un composé antioxydant choisi dans le groupe constitué par: (i) au moins une diphénylamine du groupe constitué par ladite diphénylamine à substitution alkyle et la diphénylamine à substitution aralkyle; (ii) au moins un phénol à entrave stérique; et (iii) une combinaison de (i) et (ii). L'invention porte également sur des compositions de polyéthylène stabilisées dans lesquelles est incorporée la composition stabilisante décrite ci-dessus.
PCT/US1995/011447 1994-09-13 1995-09-11 Stabilisation des polymeres de polyethylene Ceased WO1996008532A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30512794A 1994-09-13 1994-09-13
US08/305,127 1994-09-13

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WO1996008532A1 true WO1996008532A1 (fr) 1996-03-21

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999032549A1 (fr) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Utilisation de polymeres d'ethylene stabilises par des amines a empechement sterique ou pour produire des corps moules en matieres plastiques pour le stockage/transport d'esters d'huile vegetale
US6030986A (en) * 1995-02-28 2000-02-29 Eli Lilly And Company Benzothiophene compounds, intermediates, compositions, and methods
ES2166691A1 (es) * 2000-01-27 2002-04-16 Catalana Del Paper S L Procedimiento para la fabricacion de una lamina en material plastico con burbujas, para embalaje y producto obtenido.
WO2006124226A1 (fr) 2005-05-19 2006-11-23 Chemtura Corporation Melange stabilisateur destine a ameliorer la resistance au chlore
WO2005056657A3 (fr) * 2003-12-04 2007-09-27 Dow Global Technologies Inc Matiere a base de polyethylene stabilise
US7855246B2 (en) 2007-12-05 2010-12-21 Uponor Innovation Ab Plastic pipe made of polyolefin
WO2020242941A1 (fr) * 2019-05-24 2020-12-03 Si Group Usa (Usaa), Llc Mélange d'antioxydants pour caoutchoucs de polymérisation en émulsion

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520149A (en) * 1983-12-01 1985-05-28 Gaf Corporation Elastomer compositions
NL8403880A (nl) * 1984-12-21 1986-07-16 Akzo Nv Gestabiliseerde copolyetherestersamenstelling.
EP0274200A2 (fr) * 1986-12-11 1988-07-13 UNIROYAL CHEMICAL COMPANY, Inc. Polyoléfines stabilisées contre la dégradation oxydative avec des mélanges de diarylamines aralkylées et de phénols stériquement encombrés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520149A (en) * 1983-12-01 1985-05-28 Gaf Corporation Elastomer compositions
NL8403880A (nl) * 1984-12-21 1986-07-16 Akzo Nv Gestabiliseerde copolyetherestersamenstelling.
EP0274200A2 (fr) * 1986-12-11 1988-07-13 UNIROYAL CHEMICAL COMPANY, Inc. Polyoléfines stabilisées contre la dégradation oxydative avec des mélanges de diarylamines aralkylées et de phénols stériquement encombrés

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6030986A (en) * 1995-02-28 2000-02-29 Eli Lilly And Company Benzothiophene compounds, intermediates, compositions, and methods
WO1999032549A1 (fr) * 1997-12-18 1999-07-01 Basf Aktiengesellschaft Utilisation de polymeres d'ethylene stabilises par des amines a empechement sterique ou pour produire des corps moules en matieres plastiques pour le stockage/transport d'esters d'huile vegetale
US6548580B1 (en) 1997-12-18 2003-04-15 Basf Aktiengesellschaft Use of sterically hindered amines or stabilised ethylene polymers in the production of plastic bodies for storage and transport of vegetable oil esters
ES2166691A1 (es) * 2000-01-27 2002-04-16 Catalana Del Paper S L Procedimiento para la fabricacion de una lamina en material plastico con burbujas, para embalaje y producto obtenido.
RU2375388C2 (ru) * 2003-12-04 2009-12-10 Дау Глобал Текнолоджиз Инк. Стабилизированный полиэтиленовый материал
WO2005056657A3 (fr) * 2003-12-04 2007-09-27 Dow Global Technologies Inc Matiere a base de polyethylene stabilise
US7744972B2 (en) * 2003-12-04 2010-06-29 Dow Global Technologies Inc. Stabilized polyethylene material
AU2004297227B2 (en) * 2003-12-04 2010-09-23 Dow Global Technologies Llc Stabilized polyethylene material
US8163226B2 (en) 2003-12-04 2012-04-24 Dow Global Technologies Llc Stabilized polyethylene material
WO2006124226A1 (fr) 2005-05-19 2006-11-23 Chemtura Corporation Melange stabilisateur destine a ameliorer la resistance au chlore
US7855246B2 (en) 2007-12-05 2010-12-21 Uponor Innovation Ab Plastic pipe made of polyolefin
WO2020242941A1 (fr) * 2019-05-24 2020-12-03 Si Group Usa (Usaa), Llc Mélange d'antioxydants pour caoutchoucs de polymérisation en émulsion
JP2022534492A (ja) * 2019-05-24 2022-08-01 エスアイ グループ スイッツァランド （シーエイチエイエイ） ゲゼルシャフト ミット ベシュレンクテル ハフツング 乳化重合ゴム用の酸化防止剤ブレンド

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