[go: up one dir, main page]

WO2000009604A1 - Composition de plastique a resistance aux intemperies accrue - Google Patents

Composition de plastique a resistance aux intemperies accrue Download PDF

Info

Publication number
WO2000009604A1
WO2000009604A1 PCT/NL1999/000506 NL9900506W WO0009604A1 WO 2000009604 A1 WO2000009604 A1 WO 2000009604A1 NL 9900506 W NL9900506 W NL 9900506W WO 0009604 A1 WO0009604 A1 WO 0009604A1
Authority
WO
WIPO (PCT)
Prior art keywords
tetramethyl
plastic composition
piperidinyl
bis
bridgehead
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/NL1999/000506
Other languages
English (en)
Inventor
Pieter Gijsman
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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
Application filed by DSM NV filed Critical DSM NV
Priority to AU53879/99A priority Critical patent/AU5387999A/en
Priority to EP99939622A priority patent/EP1114096A1/fr
Publication of WO2000009604A1 publication Critical patent/WO2000009604A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring

Definitions

  • the invention relates to a plastic composition containing a polymer and at least one hindered amine light stabiliser.
  • a hindered amine light stabiliser will be called a 'HALS compound' .
  • a plastic composition containing a polymer and at least one HALS compound is known from US-A-
  • Patent US-A-3.90 .581 describes a plastic composition that contains a polymer and a 4-amino- piperidine compound, being a HALS compound, as a result of which the plastic composition is stabilised against degradation under the influence of heat and light. It is commonly known that stabilising a plastic composition against degradation under the influence of heat and light, in particular against degradation under the influence of Uv " radiation, causes the plastic composition's weather resistance to improve, as a result of which the plastic composition becomes suitable for certain applications, for example for outdoor applications.
  • the aim of the invention is to provide a plastic composition having such improved weather resistance.
  • This aim is achieved according to the invention in that the plastic composition according to the invention contains a polymer, at least one HALS compound and at least one bridged amine compound containing at least one N bridgehead.
  • a plastic composition that contains a polymer, at least one HALS compound and at least one bridged amine compound containing at least one N bridgehead exhibits a weather resistance that is substantially better than that of the known plastic composition that does not contain the bridged amine compound containing at least one N bridgehead. It was also found that a plastic composition that contains a polymer, at least one HALS compound and at least one bridged amine compound containing at least one N bridgehead has a weather resistance that is better than the sum of the contributions of the HALS compound and the bridged amine compound would suggest. This is all the more surprising in that it has also been found that a plastic composition that contains a polymer and only one bridged amine compound is scarcely stabilised against degradation under the influence of heat and light. With certain choices of the components of the plastic composition according to the invention it was for example found that the weather resistance of the plastic composition according to the invention sometimes showed a weather resistance that was more than double the weather resistance of the known plastic compositions .
  • a Xenon test is used as a measure of the weather resistance.
  • the Xenon test determines a plastic composition's resistance to degradation under the influence of light from a filtered (borosilicate glass) Xenon lamp at a black panel temperature of 62°C with an intensity of 0.35 W.m “ .nm “1 , at a wavelength of 340 nm and at a relative humidity of 55 vol . % in a wet/dry cycle of 18 minutes wet and 102 minutes dry.
  • the degradation of the plastic composition is measured as the difference between the carbonyl absorption at 1713 cm “1 and the absorption at 1860 cm “1 as a function of the length of time for which the plastic composition is subjected to said combination of light, temperature and humidity.
  • the weather resistance is expressed as the difference between the measured carbonyl absorptions of the films before and after 2500 hours' ageing according to said combination of light, temperature and humidity.
  • a 'hindered amine light stabiliser' is understood to be compounds having the following general formulas :
  • Ri up to and including R 5 are independent substituents .
  • suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination hereof.
  • a hindered amine light stabiliser may also form part of a polymer.
  • a compound derived from a substituted piperidine compound is chosen as the HALS compound, in particular any compound derived from an alkyl-substituted piperidyl, piperidinyl or piperazinone compound and substituted alkoxypiperidinyl compounds. Examples of such compounds are
  • HALS PB-41 (Clariant Huningue S.A.); - Nylostab ® S-EED (Clariant Huningue S.A.); 3-dodecyl-l- (2,2,6, 6 -tetramethyl -4 -piperidyl) - pyrrolidin-2 , 5-dione; Uvasorb ® HA88;
  • HALS 7 D-glucitol, 1, 3 : 2 , -bis-O- (2 , 2 , 6, 6-tetramethyl-4- piperidinylidene) (HALS 7) ; - oligomer of 7-oxa-3,20- diazadispiro [5.1.11.2] heneicosan-21-one, 2 , 2,4,4- tetramethyl-20- (oxiranylmethyl) (Hostavin ® N30) ;
  • the bridged amine compound containing at least one N bridgehead that can be used in the context of this invention is preferably a compound derived from a compound having the general formulas
  • M x to M 4 are bridgeheads and the individual bridgeheads are chosen independently of one another from the group comprising carbon, nitrogen, silicon and phosphorus, it being understood that at least one bridgehead must always be a nitrogen atom and carbon and silicon may be substituted;
  • N bridgehead is defined as a bridgehead that is a nitrogen atom;
  • Di, D m , D n , D 0 , D p and D q here each represent a chain with a length of from 1 to 20 atoms, the number of atoms of which the chains are composed being equal to l,m,n,o,p and q, it being possible to choose each number and type of atoms independently of one another and it being possible for the chains to have different lengths and to be composed of different types of atoms.
  • the chains may also contain side groups, the number of atoms in the side groups not being included in the number of atoms in the chain. Suitable choices for atoms of which the chains may be composed are carbon, nitrogen, oxygen, silicon and phosphorus. Preferably the chains are composed of from 1 to 3 carbon atoms .
  • the bridged amine compound containing at least one N bridgehead is used with a HALS compound in a ratio, relative to the amount of HALS compound, of between approximately 1:20 (m.-m) and approximately 20:1 (rrt:m) , more preferably in a ratio of between approximately 1:10 (m:m) and approximately 10:1 (m:m) , most preferably in a ratio of between approximately 1:5 (m:m) and approximately 5:1 (m:m) .
  • the weather resistance is better than would be expected on the basis of the contained amounts of the bridged amine compound containing at least one N bridgehead and the HALS compound.
  • the amount of bridged amine compound containing at least one N bridgehead that can be used in the plastic composition may vary within a wide range, which can easily be determined by an average person skilled in the art.
  • the range may vary in accordance with for example the type of polymer, the type of HALS compound, the other additives in the additives package, the weather resistance to be achieved or in general the type, the properties and the specific application of the plastic composition.
  • the bridged amine compound containing at least one N bridgehead to be present in the plastic composition in an amount, relative to the amount of polymer in the plastic composition, of between preferably approximately 0.01 wt.% and approximately 10.0 wt.%, more preferably in an amount of between 0.05 wt.% and 5 wt.%, most preferably in an amount of between 0.1 wt . % and 2.5 wt . % .
  • R and R' are independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof.
  • the substituent may moreover connect several compounds I and/or II to one another.
  • - derivatives obtained in a reaction of 7-amino-l, 3 5- triazadamantane with compounds which one or more functional groups. Examples of these functional groups are aldehydes, acids, esters, amides, ketones, anhydrides and isocyanates .
  • - triazadamantane derivatives that are bound to a polymer (preferably a polyolefin) with the aid of an imide functionality;
  • HMTA - hexamethylenetetra ine
  • DABCO diazabicyclo [2.2.2] - octane
  • HMTA and DABCO are commercially readily available or can be easily prepared using commonly known processes.
  • HMTA can for example be easily prepared from the cheap, readily available basic raw materials ammonia and formaldehyde.
  • the bridged amine compound containing at least one N bridgehead is preferably used as a salt, more preferably as an ammonium salt in combination with a HALS compound having a molecular weight of less than 1000 g/mol.
  • a carboxylic acid is chosen as a salt former.
  • suitable carboxylic acids are aliphatic carboxylic acids, aliphatic dicarboxylic acids and aromatic carboxylic acids. Suitable choices are stearic acid, sebacic acid, cyclohexanedicarboxylic acid and benzenetricarboxylic acid.
  • the bridged amine compound containing at least one N bridgehead is not used as a salt if the salt former contains a halogen or sulphur, it being commonly known that compounds containing halogen or sulphur can reduce the effect of the HALS stabiliser.
  • the bridged amine compound containing at least one N bridgehead is substituted with at least one substituent having a molecular weight preferably of at least 50, more preferably of at least 100.
  • the plastic composition according to the invention preferably contains a thermoplastic polymer chosen from the group consisting of polyolefins and styrene polymers. Suitable choices are for example
  • propylene polymers such as propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer and mixtures hereof.
  • propylene polymers in the context of this invention are mixtures containing at least 50 wt.% of one of the aforementioned propylene polymers with for example polyethylene or ethylene-propylene-diene copolymers ;
  • ethylene polymers such as low-density polyethylene (LDPE) , high-density polyethylene (HDPE) , very-low- density polyethylene (VLDPE) , linear-low-density polyethylene (LLDPE) or ultra-high-molecular-weight polyethylene (UHMWPE) ;
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • VLDPE very-low- density polyethylene
  • LLDPE linear-low-density polyethylene
  • UHMWPE ultra-high-molecular-weight polyethylene
  • styrene polymers such as polybutylene-1.
  • styrene polymers are for example polystyrene, high-impact-resistant polystyrene (HIPS) , styrene-acrylonitrile copolymer (SAN) , acrylonitrile- butadiene-styrene copolymer (ABS) , styrene-maleic anhydride copolymer (SMA) and styrene-maleimide copolymer (SMI) .
  • HIPS high-impact-resistant polystyrene
  • SAN styrene-acrylonitrile copolymer
  • ABS acrylonitrile- butadiene-styrene copolymer
  • SMA styrene-maleic anhydride copolymer
  • SMI styrene-maleimide copolymer
  • the polymer is a propylene polymer or an ABS, even more
  • the bridged amine compound containing at least one N bridgehead can easily, and at any desired time before a plastic article, such as a moulded part, foil, film, fibre, coating, foam, tape, latex or powder, is produced from the plastic composition, be introduced into the plastic composition with the aid of one of the many standard methods known to a person skilled in the art.
  • a plastic article such as a moulded part, foil, film, fibre, coating, foam, tape, latex or powder
  • the bridged amine compound containing at least one N bridgehead for example in the form of a powder, solution, emulsion or suspension, is mixed with the other components of the plastic composition, which are in the form of for example a powder or a melt.
  • the bridged amine compound containing at least one N bridgehead is first mixed with at least one HALS compound and optionally other additives in a so-called additives package, for example in the form of a powder, solution, emulsion or suspension, and this package is subsequently added to the plastic, for example in the form of a powder or as a melt .
  • the plastic composition containing a polymer, at least one HALS compound and at least one bridged amine compound containing at least one N bridgehead may also contain other additives, for example antioxidants, thermal and UV stabilisers, metal deactivators, fillers, pigments, flame retardants, optical whitening agents and similar additives that are used in plastic compositions.
  • additives for example antioxidants, thermal and UV stabilisers, metal deactivators, fillers, pigments, flame retardants, optical whitening agents and similar additives that are used in plastic compositions.
  • a polypropylene powder (PP) was mixed with a dichloromethane solution containing an amount of a HALS compound. This mixture was dried in an oven
  • the PP composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes pressureless preheating at 190°C, after which the force was raised to 100-120 kNewton, followed by 10 minutes cooling at said pressure) .
  • the thickness was checked with a Heidenhain electronic meter.
  • the films had an average thickness of 120 -150 ⁇ m.
  • the weather resistance of a plastic composition was determined in a weather resistance test, carried out in an Atlas Material Testing Technology Weather-0 meter (type Ci65) according to the method described in the above description. The degradation was measured with the aid of FT-IR. The weather resistance is then expressed as the difference between the measured carbonyl absorptions of the films before and after 2500 hours' ageing according to the aforementioned combination of light, temperature and humidity.
  • HMTA hexamethylenetetramine.
  • HMTA stearate monosalt of stearic acid and HMTA ATADE: 7-amino-l, 3 , 5-triazadamantane dodecylidene-atade : 7-dodecylideneamino-l , 3,5- triazadamantane .
  • a series of plastic compositions was prepared using the process described above.
  • the composition of the plastic composition was varied.
  • PP was chosen as the polymer (Stamylan R , type P83ml8, DSM, the Netherlands) .
  • Films were produced from the plastic compositions using the process described above. The films were subjected to a weather resistance test and the weather resistance was determined as described above. The results are summarised in Table 1.
  • Table 1 Weather resistance of various compounds containing different HALSes and bridged amines
  • the plastic composition according to the invention preferably contains a salt of a bridged amine compound containing at least one N bridgehead and a HALS compound having a molecular weight of less than 1000 g/mol, or a bridged amine compound containing at least one N bridgehead which is not a salt and a HALS compound having a molecular weight of more than 1000 g/mol.

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 une composition de plastique contenant un polymère, au moins un photostabilisant aminé empêché (composé HALS) et au moins un composé aminé ponté, contenant au moins une tête de pont N. Ladite composition contient, de préférence, un sel d'un composé aminé ponté, comprenant au moins une tête de pont N et un composé HALS possédant un poids moléculaire de moins de 1 000 g/mol, ou un composé aminé ponté contenant au moins une tête de pont N différente d'un sel et un composé HALS possédant un poids moléculaire de plus de 1 000 g/mol.
PCT/NL1999/000506 1998-08-12 1999-08-09 Composition de plastique a resistance aux intemperies accrue Ceased WO2000009604A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU53879/99A AU5387999A (en) 1998-08-12 1999-08-09 Plastic composition with improved weather resistance
EP99939622A EP1114096A1 (fr) 1998-08-12 1999-08-09 Composition de plastique a resistance aux intemperies accrue

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1009844 1998-08-12
NL1009844A NL1009844C2 (nl) 1998-08-12 1998-08-12 Kunststofsamenstelling met een verbeterde weersbestendigheid.

Publications (1)

Publication Number Publication Date
WO2000009604A1 true WO2000009604A1 (fr) 2000-02-24

Family

ID=19767636

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000506 Ceased WO2000009604A1 (fr) 1998-08-12 1999-08-09 Composition de plastique a resistance aux intemperies accrue

Country Status (4)

Country Link
EP (1) EP1114096A1 (fr)
AU (1) AU5387999A (fr)
NL (1) NL1009844C2 (fr)
WO (1) WO2000009604A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1571177A1 (fr) * 2004-03-03 2005-09-07 DSM IP Assets B.V. Elastomeres avec résistance aux intempéries ameliorée
WO2015167423A1 (fr) * 2014-04-28 2015-11-05 Aquadye Fibers, Inc. Fils à base d'oléfine teints à basse température et tissus textiles utilisant de tels fils

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2545292A1 (de) * 1975-10-09 1977-04-14 Hoechst Ag Azaadamantanverbindungen als stabilisatoren fuer organische polymerisatzusammensetzungen
DE2637193A1 (de) * 1976-08-18 1978-02-23 Hoechst Ag Neue derivate des 7-amino-1,3,5- triazaadamantans als lichtschutzmittel
EP0476612A2 (fr) * 1990-09-18 1992-03-25 GREAT LAKES CHEMICAL ITALIA S.r.l. Mélange stabilisant pour composés ayant une activité photochromatique
WO1998036023A1 (fr) * 1997-02-12 1998-08-20 Dsm N.V. Composition de matieres plastiques presentant une resistance accrue aux intemperies

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2545292A1 (de) * 1975-10-09 1977-04-14 Hoechst Ag Azaadamantanverbindungen als stabilisatoren fuer organische polymerisatzusammensetzungen
DE2637193A1 (de) * 1976-08-18 1978-02-23 Hoechst Ag Neue derivate des 7-amino-1,3,5- triazaadamantans als lichtschutzmittel
EP0476612A2 (fr) * 1990-09-18 1992-03-25 GREAT LAKES CHEMICAL ITALIA S.r.l. Mélange stabilisant pour composés ayant une activité photochromatique
WO1998036023A1 (fr) * 1997-02-12 1998-08-20 Dsm N.V. Composition de matieres plastiques presentant une resistance accrue aux intemperies

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALLEN, N.S.: "Photostabilizing performance of a hindered piperidine compd.---", POLMER DEGRADATION AND STABILITY, vol. 2, no. 2, 1980, pages 129 - 135, XP002068337 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1571177A1 (fr) * 2004-03-03 2005-09-07 DSM IP Assets B.V. Elastomeres avec résistance aux intempéries ameliorée
WO2015167423A1 (fr) * 2014-04-28 2015-11-05 Aquadye Fibers, Inc. Fils à base d'oléfine teints à basse température et tissus textiles utilisant de tels fils

Also Published As

Publication number Publication date
EP1114096A1 (fr) 2001-07-11
AU5387999A (en) 2000-03-06
NL1009844C2 (nl) 2000-02-15

Similar Documents

Publication Publication Date Title
US4459395A (en) Piperidyl derivatives of triazine copolymers, processes for their preparation and stabilized composition containing these derivatives
US3542729A (en) Stabilization of synthetic polymers
TW580512B (en) Synergistic stabilizer mixture based on polyalkyl-1-oxa-diazaspirodecane compounds
US4547548A (en) Polymeric compounds containing piperidine and triazine radicals, process for their preparation, and their use as stabilizers for synthetic polymers
CA2181665C (fr) Melange stabilisateur synergiste
EP0000769B1 (fr) Polymères contenant des groupements polyalkylpipéridine et leur utilisation comme stabilisants
AU6123198A (en) Plastics composition having improved weather resistance
WO2000009604A1 (fr) Composition de plastique a resistance aux intemperies accrue
EP0082738B1 (fr) Sels d'amino-peroxydes et leurs utilisations
GB2345485A (en) Sterically hindered amines as stabilisers to actinic radiation in polymers
EP0392759A1 (fr) Composition polymère photodégradable
JPS61500123A (ja) 安定化した熱可塑性ポリマ−組成物
NL1008680C2 (nl) Kunststofsamenstelling met een verbeterde weersbestendigheid.
US4710527A (en) Malonate-based light stabilizers for plastics
AU593025B2 (en) Tartrate-based compound useful as stabilizers for polymers
ES2251695T3 (es) Composicion de resina de polipropileno estabilizada.
US4471417A (en) Poly-bis-triazinylimides, their preparation
EP1571177A1 (fr) Elastomeres avec résistance aux intempéries ameliorée
MXPA99007440A (en) Plastics composition having improved weather resistance
JPH04222851A (ja) ポリアセタール重合体組成物
CN114605624A (zh) 一种聚合型光稳定剂以及制备与应用
EP0219332B1 (fr) Composés tartriques comme agents de stabilité à la lumière de matières plastiques
US3898303A (en) Piperidine-spiro-hydantoin derivatives and their use as stabilizers
WO2020058337A1 (fr) Utilisation d'un composé à base de mélamine et d'un composé hals utilisé comme stabilisant thermique dans des polymères
CA1244597A (fr) Amines polymeres comportant un empechement sterique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE 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 MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
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: 1999939622

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999939622

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999939622

Country of ref document: EP