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WO1996038499A1 - Antioxydants contenant une amine pour polymeres - Google Patents

Antioxydants contenant une amine pour polymeres Download PDF

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Publication number
WO1996038499A1
WO1996038499A1 PCT/US1996/008162 US9608162W WO9638499A1 WO 1996038499 A1 WO1996038499 A1 WO 1996038499A1 US 9608162 W US9608162 W US 9608162W WO 9638499 A1 WO9638499 A1 WO 9638499A1
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WO
WIPO (PCT)
Prior art keywords
amine
bis
phosphite
polymer
amount
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/US1996/008162
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English (en)
Inventor
William E. Wright
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.)
Paxon Polymer Co LP
Original Assignee
Paxon Polymer Co LP
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Filing date
Publication date
Application filed by Paxon Polymer Co LP filed Critical Paxon Polymer Co LP
Publication of WO1996038499A1 publication Critical patent/WO1996038499A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

Definitions

  • the present invention relates to antioxidants for polymers and more particularly to mixtures of antioxidants and amines for chromium catalyzed high density polyethylene (HDPE) polymers.
  • HDPE high density polyethylene
  • HDPE polymers are subject to oxidative degradation in the presence of atmospheric oxygen and moisture.
  • organic phosphites are used by those skilled in the art in order to stabilize organic polymers against the oxidative degradation caused by light and/or heat in the presence of atmospheric oxygen and moisture.
  • One particularly important property of phosphites is that they suppress color formation during HDPE processing.
  • Their mode of action includes reaction with hydroperoxides that form through oxidation of the polymer. For example, in the oxidation of polyolefins, alkyl hydroperoxides form through a sequence of reactions involving the intermediate formulation of free radicals. The alkyl hydroperoxides then attack more polymer chains to produce still more free radicals thus leading to further degradation of the polymer.
  • Phosphites are particularly effective in decomposing hydroperoxides thus terminating the chain reactions.
  • Such organic phosphites are disclosed in U.S. patents 3,516,963 and 4,305,866.
  • Unfortunately, these organic phosphites are known to undergo degradation during storage conditions. Phosphites are very reactive with water and oxygen and can decompose to yield products that are ineffective in suppressing degradation. In this process they are converted into inactive compounds and are then no longer effective as antioxidants.
  • the stability of phosphites appears to be even poorer in the presence of chromium and therefore residual chromium in HDPE produced with chromium catalysts can cause the phosphite to degrade faster.
  • patent 3,922,249 discloses a stabilized antistatic composition for polyolefins which requires adding a preformed admixture of a hindered phenol thermal stabilizer, a tertiary amine antistatic agent and a phosphite which prevents discoloration of the antistatic agent prior to blending with the polyolefin. All of the foregoing patents are incorporated herein by reference.
  • phosphites that may be present in HDPE produced using chromium catalysts are particularly susceptible to degradation. Such degradation is apparently not a problem with HDPE produced with Ziegler type catalysts since they show better phosphite retention under severe storage conditions of high heat and relative humidity.
  • chromium catalyzed HDPE As the phosphite level decreases, the net hydrolysis products are found at ever increasing levels. Since chromium catalyzed HDPE is more advantageous than Ziegler catalyzed HDPE with respect to molecular weight distribution and toughness for certain applications such as blow molding, it would be desirable to solve the degradation problem in chromium catalyzed HDPE.
  • chromium catalyzed HDPE may be stabilized against such oxidative degeneration by forming a melt of the HDPE and then adding thereto an ethoxylated C ⁇ 2 to Cjg alkyl amine and a dicycloalkyldiphosphite.
  • the amine additive significantly increases phosphite retention. This is achieved effectively by adding a small amount of an ethoxylated amine to the phosphite containing polymer during pelletization of the HDPE.
  • Ethoxylated amines have long been used as antistatic agents in polymers, but for this application they must be used at relatively high concentrations. Thus their use at lower levels for the purpose of suppressing phosphite degradation is unexpected in the art of polymer additives.
  • the invention provides a composition which comprises (a) a chromium catalyzed high density polyethylene polymer which undergoes oxidative degradation in the presence of atmospheric oxygen and water; and (b) at least one phosphite capable of hindering, and in an amount sufficient to hinder, the oxidative degradation of the polymer; and (c) at least one ethoxylated C j 2 to C j g alkyl amine capable of hindering, and in an amount sufficient to hinder, the hydrolysis of the phosphite.
  • composition of this invention is prepared which provides a means for suppressing the loss of phosphite antioxidants when they are blended as stabilizers in pelletized, chromium catalyzed HDPE polymers.
  • High density polyethylenes are well known in the art and generally refers to those having densities in the range of from 0.94 to 0.965 grams per cubic centimeter.
  • polyethylene includes homopolymers of ethylene and copolymers of at least 85 weight percent ethylene with up to 15 weight percent of one or more C3 to CJQ alpha- olefins, such as 1-butene, 1-hexene, etc.
  • the copolymers include from 0.1 to 3 weight percent of the alpha-olefin comonomer.
  • the polyethylene preferably has a melt flow index, as measured by the procedures of ASTM D-1238, condition E, of from 0.1 to 100 decigrams per minute, more preferably from 0.1 to 30 decigrams per minute.
  • Suitable chromium catalyzed high density polyethylenes non-exclusively include those having a number average molecular weight in the range of from 10,000 to 500,000, preferably from 20,000 to 100,000.
  • Preferred chromium catalyzed high density polyethylenes are commercially available from Paxon Polymer Company of Baton Rouge, Louisiana.
  • Suitable phosphites are those which are in solids at room temperature, and which can be made into paniculate form including granules, pastilles, powders and other particulates, preferably in a powder forms.
  • Suitable phosphites may be defined by the general formula
  • R 3 O wherein R 1 , R 2 and R- represent either the same or different hydrocarbyl radicals, which can be either substituted or non-substituted alkyl, cycloalkyl, aryl, alkaryl or aralkyl radicals.
  • trialkyl phosphites dialkyl monophenyl phosphites, diphenyl monoalkyl phosphites and triphenyl phosphates, optionally bearing hydrocarbyl substituents on the benzene ring, are useful phosphite stabilizers.
  • Dicycloalkyldiphosphites are preferred.
  • organic phosphites are diphenyl-2-ethylhexyl phosphite, triphenyl phosphite, tris(2,5 di-tert-butyl-phenyl)phosphite, tris(2-tert-butyl- phenyl)phosphite, tris(2-phenylphenyl)phosphite, tris[2-(l, l-dimethylpropyl]phosphate, tris(2-cyclohexylphenyl)phosphite, tris(2-tert-butyl-4-phenylphenyl)phosphite, tris(2- tert-butyl-4-methylphenyl)phos ⁇ hite, tris(2,4-tert-amylphenyl)phosphite, tris(2,4-di- tert-butylphenyl)phosphite, and 2,2-methylene-bis(4, 6-di
  • each R 4 radical is the same or different and represent hydrocarbyl radicals, which can be either substituted or non-substituted alkyl, cycloalkyl, aryl, alkaryl or aralkyl radicals.
  • organic phosphites are bis(2,4-di-tert- butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl- methylphenyl)pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite.
  • the phosphite component is preferably present in an amount of at least 0.005% to 5% by weight of the HDPE polymer.
  • a more preferred range is from 0.01% to .5% based on weight of the polymer, and most preferably from 0.05% to 0.2% based on weight of the polymer.
  • the composition contains an ethoxylated C ⁇ to Ci g alkyl amine.
  • Suitable ethoxylated amines include bis (2-hydroxyethyl)tallow amine, bis(2-ethoxyethyl) cocoamine; bis (2-hydroxyethyl)oleyl amine and bis(2-ethoxyethyl) stearyl amine and bis(2-ethoxyethyl) dodecanamine which are respectively available as Armostat 310, 410, 710, 1800 and 2000 from Akzo Nobel.
  • Bis (2-hydroxyethyl) oleyl amine is also available commercially as Chemstat 172 from Chemax.
  • the ethoxylated amine is preferably present in an amount of at least 0.005% by weight of the HDPE polymer.
  • a more preferred range is from 0.01% to 0.15% and most preferably from 0.01 % to less than 0.02 %.
  • the composition may optionally contain other conventional additives which are typically used in the compounding of HDPE, such as thermal stablilizers, for example hindered phenolics, pigments such as titanium dioxide and carbon black, fillers such as mica, talc and mixtures thereof, antioxidants, rubbers, antistatic agents, extrusion aids, UV stabilizers, lubricants, fillers, and the like, in amounts which are easily determined by those skilled in the art.
  • thermal stablilizers for example hindered phenolics, pigments such as titanium dioxide and carbon black
  • fillers such as mica, talc and mixtures thereof, antioxidants, rubbers, antistatic agents, extrusion aids, UV stabilizers, lubricants, fillers, and the like, in amounts which are easily determined by those skilled in the art.
  • compositions of this invention can be prepared by any conventional technique. They can be dry or melt blended in one or more steps. Preferably they are melt blended in standard commercial extruders or blenders.
  • the mixture was then subjected to three consecutive extrusions at 230 °C using a 2.54 cm (1 H ) diameter Rheomex 259 single screw extruder 25:1 length to diameter ratio operating at 60 rpm.
  • 200 g of the pelletized extrudate were placed in a one liter beaker equipped with a loosely fitting lid and containing a large number of holes to allow easy ingress of hot moist air.
  • the beaker was then placed in an oven which was kept at 60 °C (140 °F) and through which moist air was circulated continuously.
  • the unused three kilograms of powder was divided into three equal portions and small amounts of bis (2-hydroxyethyl)oleyl amine were added to each to give powders containing 100 ppm, 200 ppm and 300 ppm. Each of these powders was extruded three times to give three pelletized products: B (100 ppm), C (200 ppm) and D (300 ppm). 200 grams of each of the pelletized products was subjected to storage at 140 °F in an atmosphere of moist air.
  • the data shows the strong protection offered by the compound bis (2- hydroxyethyl)oleyl amine to the phosphite.

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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

L'invention concerne une composition servant à stabiliser des polymères de polyéthylène haute densité, produits au moyen d'un catalyseur au chrome, pour empêcher leur dégénération oxydative. Ladite composition comprend un phosphite et au moins une alkylamine C12 à C18 éthoxylée. Le phosphite peut empêcher la dégradation oxydative du polymère et l'amine peut empêcher l'hydrolyse du phosphite.
PCT/US1996/008162 1995-06-01 1996-05-31 Antioxydants contenant une amine pour polymeres Ceased WO1996038499A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US45718795A 1995-06-01 1995-06-01
US08/457,187 1995-06-01

Publications (1)

Publication Number Publication Date
WO1996038499A1 true WO1996038499A1 (fr) 1996-12-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/008162 Ceased WO1996038499A1 (fr) 1995-06-01 1996-05-31 Antioxydants contenant une amine pour polymeres

Country Status (2)

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AR (1) AR002149A1 (fr)
WO (1) WO1996038499A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018217772A1 (fr) * 2017-05-25 2018-11-29 Chevron Phillips Chemical Company Lp Procédés pour l'amélioration de la stabilité de la couleur dans des résines de polyéthylène

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825721A (en) * 1953-01-27 1958-03-04 Phillips Petroleum Co Polymers and production thereof
US3922249A (en) * 1973-04-12 1975-11-25 Phillips Petroleum Co Stabilized antistatic compositions useful with olefin polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2825721A (en) * 1953-01-27 1958-03-04 Phillips Petroleum Co Polymers and production thereof
US3922249A (en) * 1973-04-12 1975-11-25 Phillips Petroleum Co Stabilized antistatic compositions useful with olefin polymers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018217772A1 (fr) * 2017-05-25 2018-11-29 Chevron Phillips Chemical Company Lp Procédés pour l'amélioration de la stabilité de la couleur dans des résines de polyéthylène
CN110637053A (zh) * 2017-05-25 2019-12-31 切弗朗菲利浦化学公司 改善聚乙烯树脂颜色稳定性的方法
US10703886B2 (en) 2017-05-25 2020-07-07 Chevron Phillips Chemical Comany LP Methods for improving color stability in polyethylene resins
US11401405B2 (en) 2017-05-25 2022-08-02 Chevron Phillips Chemical Company Lp Methods for improving color stability in polyethylene resins

Also Published As

Publication number Publication date
AR002149A1 (es) 1998-01-07

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