CA2034515A1

CA2034515A1 - Stabilised polymers and their preparation

Info

Publication number: CA2034515A1
Application number: CA002034515A
Authority: CA
Inventors: Neil S. Davidson; Hilda A. Leiper; Colette A.A. Di Murro; Kenneth Wilkinson
Original assignee: BP Chemicals Ltd
Current assignee: BP Chemicals Ltd
Priority date: 1990-01-20
Filing date: 1991-01-18
Publication date: 1991-07-21
Also published as: EP0442614A3; KR910014444A; AU6981991A; IN180368B; AU641207B2; US5304589A; GB9001367D0; EP0442614A2; JPH04252247A; KR100215536B1

Abstract

ABSTRACT OF THE DISCLOSURE
STABILIZED POLYMERS AND THEIR PREPARATION

Oxidatively stabilized polyolefin polymers containing an antioxidant are made more resistant to loss of antioxidant by converting at least some of the antioxidant comprising a polymer of dicyclopentadiene and a phenolic compound into a form non extractable with cyclohexane. The conversion is preferably by reaction in the melt phase in the presence of a radical initiator. Addition of organotin esters, sulphides, oxides or thioethers reduces the colour.

Description

Case7386(2) ~C~3~5~

STABILIZED POLYMERS AND THEIR PREPARATION

~ his invention relates to stabilized polymers and their preparation and use.
The effectiveness of low molecular weight antioxidants in the stabilisation of polymers is often diminished in service by their ease of migration to the surface and extraction from the polymer. The problem of ease of migration and extraction can be reduced by the use a variety of higher molecular weight antioxidants but as their molecular weight increases, so compatibility with the base polymer tends to deerease, thus reducing their s~abilising effect.
10 US~ 4213092 describes graftinB polymers with antioxidants or UV
stabilizers especially ones with ethylenic unsaturation or a thiol group, in the presence of a free radical generator; with low density polyethylene the free radicals may be made instead in the melt with air or by high shear. It has been found that without the free radical generator melt grafting of phenolic antioxidants in the polymer tends to be low so extraction of additive is high while with the generator polyethylene tends to be cross linked.
Incorporation of an antioxidant polymer from dicyclopentadiene and a phenolic compound with the polyolefin eg by melt processing in the presence of a radical initiator has now been found as a method of providing an improved stabilized polymer.
According to the present invention there is provided an oxidatively stabilized polymer composition comprising an olefin polymer and an antioxidant characterised in that the antioxidan~
comprises a polymer of dicyclopentadiene and a phenolic compound, 2~3~
at least some of the said an~ioxidant being in a form non extractable with cyclohexane. Preferably the oxidatively stable polymer composition is obtainable by reacting in the presence of a radical initiator and in the melt phase said polyolefin and said antioxidant polymer. The invention also provides a process for obtaining said polymer by reacting the polyolefin and the said antioxidant in the presence of a radical initiator and in the melt phase.
By reacting the olefin polymer and the antioxidant polymer, the antioxidant becomes not only olefin polymar compatible but a significant proportion is also non-extractable and this may be achieved with decreased adverse effects on the polymer eg cross linking in the case of polyethylene or degra~ation in the case of polypropylene.
The olefin polymer which is usually from one or more aliphatic monom~rs, can be a homopolymer, or a copolymer obtained from two or more different monomers. Suitable homopolymers are polyethylene, polypropylene and polybutylene, preferably polyethylene. The olefin copolymers are suitably copolymers of two or more monomers which may be solely mono olefins suitably C2 to Clo olefins (for example ethylene, propylene, butylene, 4 methyl pentene-l and octene-l), or mixtures of at least one mono olefin with another ethylenically, unsaturated monomer eg vinyl alcohol, vinyl acetate and acrylic acid, methacrylic acid and their alkyl esters. Particularly preferred are homopolymers and copolymers of ethylene with a higher alpha olefin eg 25 of 3-8 carbon atoms, especially linear ones of density 915-970 kg/m3 eg 945-970 kg/m3, in particular high density polyethylenes, such as ones obtained by use of Ziegler or preferably Phillips catalysts. The level of residual unsaturation in the olefin polymer especially homopolymer and copolymers of ethylene is usually 0.1-5 eg 0.5-2 expressed as the vinyl index (the ratio of infra red absorption at 910 cm~l due to vinyl group to that at 2020 cm~l). In the ethylene copolymers the degree of branching is preferably less than 25 eg 0.01-25 such as 0.01-10 or 0.03-3 and most preferably 0.1-1 branches per 1000 carbons in the chain. In the case of polyethylene 35 particularly for use with high proportions of antioxidants eg 10 -100 3 ;~J13~5~5 parts per hundred (pph) of polymer it is preferred that linear polymers of high melt index are used eg of Melt Flow Rate (MFR) (measured as defined below) of 20-50 or 25-45 g/10 min. However, where polymers of higher olefins are used it ls preferred to use linear polymers of low melt MFR eg 1-20 g/10 min.
The antioxidant polymer comprises a polymer of dlcyclopantadiene with a phenolic compound. The phenolic compound usually has at least one and probably at least 2 of the 2, 4 and 6 positions free. The phenolic compound may be phenol itself or an alkyl phenol with 1-3 alkyl groups each of 1-6 carbon atoms, such as methyl, ethyl, isopropyl and tertiary butyl. While the phenolic compound may be an alkyl phenol with a 2-alkylsubstituent such as methyl or tertbutyl, eg as in 2-tert butylphenol and 2-tert butyl 4-methyl phenol, preferably both 2 and 6 positions are free as in the case of phenol itself and 4~alkyl phenols, which are preferred especially 4-primary or secondary alkyl phenols. The phenolic compound is most preferably phenol, para cresol (or commercial ortho/para mixtures) mixed meta/para cresol, or para ethyl phenol, especially paracresol. The phenolic compound is usually free ~f sulphur containing groups. The polymers usually contain a molar excess of units from the phenolic compound, the molar ratio of phenolic to dicyclopentadiene (DCPD) units being usually 1.1-2:1 especially 1.15-1.35:1. The polymers which are addition polymers are usually phenolic unit terminated and contain phenolic groups. They may be made by nuclear substitution of the phenolic compound by the dicyclopentadiene in the presence of a Friedel Craft catalyst usually at less than 150C. The polymers are usually substantially frae of ethylenic unsaturation derived from the dicyclopentadiene molecule and substantially free of non aromatic unsaturation. The polymers are usually substantially linear, and are multifunctional because of the presence of more than one phenolic group. The polymers preferably contain a significant proportion of molecules having at least 3 phenolic units, eg 3-10 phenolic units and/or a significant proportion of molecules having at least 2 especially 2-10 DCPD units. The polymers are preferably mixtures of polymers with at least 10% usually at least 20% of higher polymer each ~O;~lS

with 3 or more phenolic units per molecule, such as 20-80% especially 50-70%, and at most 90%, usually at most 80% of polymer with 2 phenolic units per molecule, such as 20-ôO~ especially 30-50%. The higher polymers may comprise mixtures of molecules having 3 phenolic (and 2 dicyclopentadiene) unit and 4 phenolic (and 3 dicyclopentadiene) units and 5 phenolic (and 4 dicyclopentadiene) units in weight percentages of 20-40%, 10-30% and 5-20% respectively, of the total weight of all the DCPD phenolic polymers.
When the phenolic compound has both 2 and 6 positions unsubstituted, and the polymer molecule is terminated by phenolic units it is preferred to end-cap the terminating phenolic units eg by nuclear alkylation or cycloalkylation, with a hindering group in a position ortho to the phenolic OH; examples of such hindering groups are tertiary butyl, tertiary amyl, isopropyl, alpha-methyl cyclohexyl, preferably tertiary butyl. Such polymer antioxidants are described in GB Patent 1068995, the disclosure of which is hereby incorporated by reference. Such antioxidants are available commercially under the trade name WINGSTAY L (from Goodyear).
The tert-;butylated derivatives of the DCPD polymers, especially those in which the phenol is p-cresol, preferably have pea~ melting points of at least ôO especially at least 90C such as ôO-110C or especially 90-103C such as 95-102C, have initial melting temperature of at least 70C eg 70-95C but especially at least 85C such as 85-95C, and melt at temperature somewhere in the range 70-115C especially 85-115C, and especially have not completely melted at 105C.
The reaction between the olefin polymer and the antioxidant _ polymer is carried out in the presence of a radical initiator to facilitate the incorporation of the antioxidant into the polyolefin.
The radical initiation can be effected by means of any of the conventional radical initiators especially ones only forming free radicals at a significant rate at above 120C, for example organic peroxides or hydroperoxides or azo compounds such as azobisisobutyronitrile and radiation such as ultra violet or gamma radiation, preferably organic peroxides such as dicumyl peroxide which "

.

~03451~
., : is most preferred 1,3-bis(t.butyl peroxy isopropyl benzene) or hydroperoxides such as tert butyl hydroperoxide. The level of organic peroxide is preferably with an antioxidant : peroxide weight ratio of between 4:1 to 14:1 especially 6:1 to 12:1 especially when the peroxide is dicumyl peroxide and pro rata equivalents with other peroxides and with an amount of peroxide of 0.5-10 such as 2.5-10 or 3.5-6.5 pph of polymer but especially 0.5-4.5 pph.
The reaction is preferably carried out in the melt phase typically in a melt mixer or an extruder, in which the polyolefin and antioxidant are intimately mixed in the melt phase during which period incorporation of the antioxidant into the polyolefin takes place. In the melt reaction, about 10-60% such as 15-50% eg 30-50% of antioxidant mixed with the polymer can be incorporated therein in a form which is not extractable with solvents for the antioxidant but not the polymer, specifically cyclohexane, in a Soxhlet apparatus.
The retained form may be antioxidant grafted onto the polymer or polymerized antioxidant but is usually a mixture of both, especially one with 30-70% of each type.
The temperature at which the reaction is carried out will be dependent upon the melt temperature of the polymer, but is usually 150-300C eg between 160 and 300C, preferably 160-220C eg for extruders and Banbury mixers, 200-260C or 200-250C especially 230-255C. The melt reaction is usually performed in an inert atmosphere eg under a nitrogen atmosphere.
In the melt mixing reaction, suitable rotor speeds and reaction times, and in the extrusion reaction, suitable screw speeds will be dependent upon the equipment used but suitable conditions (for example rotor speed and reaction time) for effecting substantially complete mixing will be readily determined by the man skilled in the art.
These conditions in this case usually correspond to occurrence of a significant proportion of, if not substantially complete, reaction.
Reaction times of 1-30 eg 1-5 or 5-30 minutes and rotor speeds of 10-300 rev per minute may be used.
Under the conditions used to incorporate the antioxidant into polyethylene, cross-linking of polyethylene is a competing reaction.

. . : , . , :

6 ~)3~5~5 It is a particular feature of the present invention that by using the dicyclopentadiene phenol antioxidant as described above with polyethylene, the cross-linking of the polyethylene may be reduced to an acceptable level thereby enabling the polyethylene to be further processed melt processed such as eg by extrusion. The extent of cross linking is indicated by the change in the melt flow index of the polyethylene after the mixing reaction, and by the degree of gel formation. The higher the ~elt Flow Rate of the polyethylene initially the lower the extent of cross linking, as is found with linear rather than non linear polyethylenes.
Thus according to a further aspect of the present invention there is provided an oxidatively stable polymer capable of being subsequently cross-linked if desired eg by free radicals and obtainable by reacting in the presence of a radical inhibitor and in the melt phase a polyolefin comprising a major proportion of polyethylene, especially linear polyethylene, and an antioxidant comprising said polymer of dicyclopentadiene and a phenolic compound.
The antioxidant can be incorporated in amounts to provide at least an eff~ctive amount eg at levels between 0.01 and 100 parts per 20 hundred (pph) based on the weight of the polymer (i.e.100 pph is 50%
by weight of total polymer plus antioxidant), preferably 0.1-100 pph but the level is especially between 3 and 60 pph, to produce a masterbatch. This masterbatch can subsequently be mixed or diluted with further amounts of one or more olefin polymers which may be the same as or different from the olefin polymer used in the masterbatch but preferably within the broad definition of the olefin polymer as described above) to give the required antioxidant concentration.
Antioxidant concentration in the final polymeric composition where no further dilution is intended eg when ready for final shaping to produce pipe, film or mouldings or coating for wire or cable or fibres, is suitably in the range 0.01 to 5 pph, preferably 0.03-3 pph.
The polymeric composition comprising olefin polymer incorporated with dicyclopentadiene phenolic compound can be used as such or after blending with conventional additives eg other antioxidants, antiblock and slip agents, UV stabilizers, fillers and blowing agents. In ;~Qi3~1S

relation to other phenolic compounds such as antioxidants and/or metal deactivators, they may be added to the olefin polymer before or after the incorporation of DCPD/phenolic polymer into the olefin polymer.
Thus if desired the reaction of the dicyclopentadiene phenolic product with olefin polymer may be performed in the presence of at least one other phenolic compound in particular a hindered phenolic compound which may be an antioxidant and/or metal deactivator. Such hindered phenols usually have at least one and preferably 2 alkyl groups ortho to the phenolic group, in particular alkyl groups with 1-8 carbons especially 4-8 carbons, such as methyl, ethyl and tertbutyl. The phenolic compounds may contain no other non hydrocarbon functional groups, but advantageously the compounds also contain at least one oxalamide or hydrazide group, optionally also with at least one carboxylate group, especially such compounds with 2 phenolic rings. Preferred phenols of this type are bis (hindered phenolic) hydrazides, e.g. ones in which the phenolic ring may be bonded directly to the NH group of the hydra7ide or via an alkylene group of 1-4 carbon atoms, e.g. methylene or ethylene as in substituted-p~opionic hydrazides. The preferred phenol is N,N'-bis[3-(3,5-di-tertbutyl-4-hydroxy phenyl)propion] hydrazide, e.g. as sold under the trade mark IRGANOX MD1024 by Ciba Geigy. The phenolic compound may be used in amount of up to 150% by weight of the dicyclopentadiene phenolic polymer, eg 50-120%. The extra hindered phenol may increase the total antioxidant capacity of the polymer, but, particularly with the substituted phenolic compounds with hydrazide or oxalamide groups, may increase the overall stability to oxygen of the polymer by acting as deactivators of metals, e.g.
transition metal catalyst residues or metals, e.g. copper from wire or cable. Preferably however the extra phenolic compound is absent so the reaction is performed with the dicyclopentadiene phenolic polymer (including alkyl or cycloalkyl derivatives thereof).
It has also been found the incorporation of the DCPD/phenol polymer into the olefin polymer tends to give discoloured products in particular in masterbatches with 10-100 pph DCPD/phenol polymer, though on dilution of the masterbatch with furthPr polymer, the colour level is quite acceptable for many uses. However it has been 8 2~3134~L5 discovered that addition to the incorporated olefin polymer eg the melt reaction product, in particular the masterbatch, of organotin carboxylate esters, sulphides, oxides or thioethers, significantly reduces the colour.
The present invention also provides a polymer composition of reduced colour which comprises (a) an oxidatively stabilized polymer composition of the invention, especially one obtainable by melt reaction in the presence of a free radical initiator, together with (b) at least one organotin compound, which is an organotin carboxylate, sulphide, oxide or thioether.
The organotin compound is usually a diorganotin compound of formula RlR2Sn(OOCR3)2 or R1R2Sn(OOCR4COOR5)2 or R1R2Sn(OOCR4C00) RlR2SnS,R1R2SnO, R1R2Sn(SR6)2 or RlR2Sn(SR7COOR)2 in which each of and R2, which are the same or different, represents an alkyl group, e.g. of 1-10 carbon atoms, e.g methyl, butyl, hexyl or octyl, or an aromatic group, e.g. an aromatic hydrocarbyl group, such as one of 6-19 carbon atoms such as phenyl, tolyl or xylyl, or an aralkyl group of 7-20 carbon atoms such as an aralkyl hydrocarbyl group such as benzyl or 2~Fhenylethyl or a cyclo aliphatic group, e.g. of 5-7 carbon atoms such as cyclohexyl, each R3 represents a group within the groups defined by Rl and R2 or may be an aliphatic ethylenically unsaturated hydrocarbyl group but is preferably an alkyl group of 6-20 carbon atoms such as n-octyl, 2-ethyl hexyl and undecyl, or a group such that the oOCR3 group is a stearate or palmitate or oleate group, R4 is a divalent organic group such as an alkylene group, e.g. of l-10 carbon atoms such as methylene, 1,2 ethylene, 1,3-propylene, 1,4 butylene or 1,6 hexylene or an aliphatic ethylenically unsaturated hydrocarbyl group, e.g. of 2-8 carbon atoms such as one of formula -CH-CH-, R5 is as defined for R3, R6 is a group within the group defined for R1 and may be the same but is preferably different therefrom, being preferably an alkyl group of 6-20 carbon atoms, e.g. 10-20 carbon atoms such as dodecyl or stearyl or an aralkyl group such as benzyl, R7 is a divalent group, preferably an alkylene group as defined for R4 and R8 is as defined for R5. In the above Eormula there may be 2 oxygen or sulphur containing groups on the tln, and in these cases the 2V~ S

two groups may be the same (as in dibutyl tin dilaurate) or different (as in dibutyl monolaurate monostearate).
Examples of the diorganotin compounds are dialkyltin dicarboxylates such as dibutyl and dioctyl tin dilaurates, dialkyl tin bis (monoalkyl maleate half esters) such as dibutyl and dioctyl tin bis ~mono 2-ethylhexyl maleate), dibutyl and dioctyl tin maleate, dibutyl and dioctyl tin bis (dodecylmercaptide) and especially dibutyl and dioctyl tin bis (2-ethylhexyl thio glycollate), and their corresponding dimethyl tin derivatives. Preferably the diorganotin compounds are mixed with a minor proportion of the corresponding mono organotin tris compounds and/or tris organotin compounds eg diorgano tin bis (thio glycollate esters) mixed with mono organotin tris (thio glycollate esters) and/or tris organotin mono thioglycollate esters;
amounts of the di organotin compounds can be 50-100% of the total of organotin compounds eg 60-80% or 80-~8% with up to 50% in total of the other organotin compounds such as 2-20% or 20-40% in total of the other compounds. The mixtures with the tris and/or mono organotin compounds are particularly important with the diorganotin compounds of formula RlR2Sn(SR7COOR8)2.
Advantageously the weight ratio of DCPD/phenol polymer to total organotin compound is 1:0.05-5 such as 1:0.1-1, especially 1:0.15-0.5.
The total amount of the above organotin compounds in the polymer composition of reduced colour is usually 10-10,000 pm, such as 50-5000 ppm eg 100-1000 and especially 150-500 ppm (based on the total weight of olefin polymer). The organotin compounds are added to the oxidatively stabilized compositions of the invention, preferably those with 10-100 pph DCPD/phenol polymer, and are melt blended therewith, advantageously when the compositions are being diluted down from masterbatches to compositions ready for final use. The melt blending can be performed in manners known per se eg in a melt mixer or extruder such as a Bambury mixer or mono or twin screw extruder, at a temperature of for example 150-250C eg 160-210C.
The polymer compositions of reduced colour are usually melt processable and can be converted eg by moulding or extrusion to form pipe, film, mouldings or coating for wire or cables, or for fibres, in particular for transparent or translucent products. Usually the melt processable polymer compositions of reduced colour are ones which remain melt processable after contact with water and therefore moisture curable polymers carrying pendant hydrolyzable silicon groups are usually substantially absent.
The invention will now be illustrated with reference to the following Examples in which an olefin polymer, a radical initiator (dicumyl peroxide (DCP) (from BDH Ltd) (except in Ex 11) and various antioxidants were mixed and heated to give polymeric products, which were tested for non extractable antioxidant content and melt flow rate (as a measure o~ cross linking) and in some cases for gel content (as a measure of cross linking) and oxygen induction time (as a measure of the stability to oxygen).
Materials The antioxidants and DCP were used as received from the suppliers without further purification. The supplier and chemical name of the antioxidants used are shown in Table A. The polyolefins were those sold under the Trade Marks RIGIDEX HD 5502 and HD 6007 supplied by BP
Chemicals Lt~; The RIGIDEX HD 5502 polyolefin was a high density polyethylene, which was an ethylene butene 1 copolymer with 1.3 branches per 1000 carbon atoms of density 953 kg/m3 and in the powder form had a Melt Flow Rate (measured as defined below) of 27.0 g/10 min and, as measured under 2.16 Kg load, an MFR of 0.2 g/10 min. The RIGIDEX HD 6007 polyolefin was a high density polyethylene which was an ethylene butene 1 copolymer with less than 0.5 branches per 1000 carbon atoms of density 960 kg/m3 and in the powder form had a Melt Flow Rate (measured as defined below) of 39 g/10 min and, as measured _ under 2.16 kg, an MFR of 0.7 g/10 min. Both ethylene copolymer had been made with a Phillips catalyst and contained about one vinyl group per polymer chain. The vinyl indices (the ratio of the infrared absorption at 910 cm~1 characteristic of vinyl to that at 2020 cm~l) were 1.31 and 1.37 for the RIGIDEX HD5502 and HD6007 respectively.

1 1 X~3~S

TABLE A

Trade Name Supplier Chemical Name Cyanox 1790 American Cyanamid 1,3,5-tris(4'-tert-butyl,5' -hydroxy-2',6'-dimethylbenzyl) isocyanurate Ethanox 330 Ethyl 1,3,5-tris(3',5'-ditert -butyl-4'-hydroxybenzyl)-2,4,6-t rimethylbenzene 10 Goodrite 3114 BF Goodrich 1,3,5-tris(3',5'-ditert-butyl-4'-hydroxybenzyl)-isocyanurate Goodrite 3125 BF Goodrich Tris((3-(3',5'-ditert-butyl-4' -hydroxybenzyl)-2 "-acetoxy-ethyl))isocyanurate 15 Hostanox 03 Hoechst Ethylene glycol bis((3,3-bis(3' -tert-butyl-4'-hydroxyphenyl) butyrate)) Irganox 1010 Ciba-Geigy Pentaerythrityltetrakis - -- (3-(3',5'ditertbutyl-4-hydroxyphenyl) propionate) Irganox 1035 Ciba-Geigy Benzenepropanoic acid, 3,5-bis (l,l-dimethylethyl)-4-hydroxy-, thiodi-2,1- ethanediyl ester Lowinox 22M46 Chemische Werke Lowi 2,2'-methylenebis(4-methyl,6 -tert-butylphenol) Topanol CA ICI 1,1,3-tris(2'-methyl-4' -hydroxy-5'-tert-butyl phenyl)butane Irganox 1076 Ciba-Geigy Stearyl beta-(3,5-ditert~
butyl-4-hydroxyphenyl)-propionate Wingstay L Goodyear Butylated Reaction Product of p-cresol and Dicyclopentadiene Vulkanox SKF Bayer Butylated Reaction Product ofp-cresol and Dicyclopentadiene 12 ~ 34~S

Santowhite ML Monsanto Butylated Reaction Product of p-cresol and Dicyclopentadlene The Wingstay L and Vulkanox products were a mixture of polymers with about 37-41g of polymer with 2 phenol and 1 DCPD units about 27-31g of polymer with 3 phenol and 2 DCPD units, about 17-21% of polymer with 4 phenol and 3 DCPD units and 10-14% of polymer with 5 phenol and 4 DCPD units and the remainder higher polymers still. The percentages were estimated from peak areas following analyses by size exclusion chromatography with W response . The Wingstay product had an average molecular weight of 600-700.
The melting proportions of the WINGSTAY, VULKANOX and SANTOWHITE
products were later determined by Differential Scanning Calorimetry.
The results were as follows.
Initial Melt Peak Melt Melting Range Pt ~C Pt ~C C
SANTO~HITE HL 75.6 83.6 75.6 - 93.9 ~INGSTAY L88.3 99.5 88.3 - 111 W LXANOX 90.4 96.6 90.4 - 101.8 Melt Proces~n~
The melt mixing reactions of Ex 1-7 and A-N were carried out in a Haake Rheocord Torque rheometer, under a nitrogen atmosphere while the extrusion reaction in Ex 8 was performed in a Leistritz twin screw ex~ruder.
Determination of Non-extractable Antioxidant The level of non extractable antioxidant, which was incorporated into the polyethylene during the melt reaction, was determined gravimetrically by Soxhlet extraction and is quoted in units of pph.
_ About 10g of product was extracted over an appropriate refluxing solvent in which the antioxidant but not the polymer was soluble, (for example cyclohexane was used in the case of the antioxidants in Ex 1-3. The extraction period was dependent upon the ease of removal of extractable antioxidant by the solvent and extraction was continued until the weight of the material undergoing extraction remainedconstant, indicating that all extractable material had been removed. Usually 12 hr extraction was sufficient. The higher the 13 Z~ 5 degree of cross linking the greater was the difficulty in extracting antioxidant.
Determination of PolYmer Melt Flow Rate (MFR) The melt flow rate of the product of the melt reaction was taken as a guide to the degree of cross-linking on the basis that the lower the NFR with respect to the base polymer the greater the extent to which cross-linking had occurred.
The MFR was measured according to ~S3412: 1976, lS01133- 1981:
condition 7, at 190C using a Davenport melt indexer with an applied load of 21.6kg the conditions under which all the MFR values in this specification are quoted, unless otherwise stated.
Example 1 The antioxidant sold under the trademark WINGSTAY L and the HDPE
RIGIDEX HD 5502 polyethylene were melt mixed in a Haake Rheocord melt mixer. The Wingstay L product was charged at 30pph (based on a hundred parts of polymer) with 5pph of Dicumyl Peroxide (DCP) also charged.
Charge = 46g Set tempera-t~re = 2501C
20 Reaction time = 10 mins Rotor speed = 55rpm The polymeric product was extracted for 12 hours with cyclohexane and the level of non-extractable antioxidant determined to be 12pph ie (40% retention relative to antioxidant originally mixed with polymer).
The MFR of the extracted polymer product = 17.0g/lOmin.
Examples 2 and 3 and Comparative Ex A-P
The antioxidant WINSTAY L of Ex 1 was replaced by each of the antioxidants Santowhite ML and Vulkanox SKF and the mixtures were otherwise processed exactly as in Example 1. The results are given in Table I.
The process was then repeated for comparative purposes with other antioxidants with the same or different amounts of initiator and the compositions obtained were tested according to the method given in Example 1. For comparison the MFR of the polyolefin after melting of Z~3~5 the powder and pelletization was also determined. The results are tabulated in Table I; any difference in level of amount of p~roxide used is indicated below.
TABLE I
COMPARISON OF DIFFERENT ANTIOXIDANTS

Antioxid~nt Level of Non-extractable ~1 6~ d Example charged at Antioxidant (g/lOmin) 30 pph level (pph) (after extraction) 1 Wingstay L 12 17 2 Santowhite ML 5 18.3 15 3 Vulkanox SKF 8 18.5 A Irganox 1010 22 Did not flow B Irganox 1035 18 Did not flow C Topanol CA 13 7.0 D ~anox 1890 12 0.3 20 E Goodrite 3114 13 Did not flow F Ethanox 330 10 0.5 G Hostanox 03 23 Did not flow H Goodrite 3125 21 Did not flow N Lo~inox 22M46 3 12.3 25 ABOVE REACTED WITH 5pph DCP
IIrganox 1010 - ¦ 20 Did not flow Ex I REACTED WITH 2.5pph DCP
_ JIrganox 1010 ¦ 23 Did not flow KHostanox 03 - ¦ 23 Did not flow 30 Ex J, K REACTED WITH lpph DCP
P None ¦ - 18.4*
Ex P had no DCP
I _ _ _ * Not extracted , ~03~5~L5 Ex 4-6 The process of Ex 1 was repeated for ~x 4 and 5 but with a set temperature for mixing at 160~C and 200C respectively. For Ex 6 the melt mix product of Ex 1 was remelted at 250C and mixed with further RIGIDEX HD 5502 polyethylene to give a polymer product having a total level of antioxidant of 1000 ppm.
The gel content was tested for the products of Ex 1 and 4-6 and the results are tabulated in Table II. The gel content analysis was based upon BS5468:1977.
TABLE II
GEL CONTENT ANALYSIS
_ _ EXAMPLE % w/w GEL

11.7 40.7 _ 50.6 6<0.1 Ex 7 In a modification of the process of Ex 6 the process of Ex 1 was repeated (to provide Ex 7) with an initial level of antioxidant in the mixer reaction of 6 pph (instead of 30 pph) and 0.95 pph DCP. The melt reaction products of Ex 1 and 7 were each divided into 2 samples - . one pair of which was extracted and the other pair not extracted;
subsequently the non extracted product samples were diluted with 221 times their weight of more RIGIDEX HD 5502 polymer down to a level of 1000 ppm antioxidant. The extracted product samples were similarly diluted with 221 parts of the same polymer. The Oxygen Induction Time OIT of the diluted products was determined at 200 C in a Stanton Redcroft STA 785 simultaneous TG/DGC apparatus. The results are shown in Table III as are those of the products of Ex 6, and are compared to ~345~5 thoss of RIGIDEX HD5502 polymer alone and to those with blend compositions of the polyolefin and 1000 ppm IRGANOX 1010 ~made in the absence of DCP) before and after extraction.
TABLE III
OXYGEN INDUCTION TIMES

OIT WITHOUT OIT WIT~
EXAMPLE EXTRACTION F.XTRACTION

10 COMP. (Q) 27.5min 1.2 min Irganox 1010 _ 1 22 min 5 min . _ 15 7 16 min 4.6 min RIGIDEX HD5502 1.2 min _ Example 8 The process of Ex 1 was repeated with 6 pph WINGSTAY L
antioxidant and RIGIDEX HD 6007 polyethylene and 0.67 pph DCP reacted in a Leistritz twin screw extruder with set temperature profile of 180-210C.
The product was extracted for 12 hours with cyclohexane and the level of non-extractable antioxidant determined to be 1.4pph.
The MFR of the extracted material = 7.3g~10min.
Example 9 _ The process of Ex 1 was repeated with a set temperature of 230C
and a homo polypropylene having an MFR (under 2.16 kg load at 230C) of 2.35 g/10 min, sold by Hoechst under the Trade Mark HOSTALEN PPN
1060F3. The level of non extractable antioxidant was determined to be 7 pph and the MRF of the extracted polymer product (measured under a 2.16 kg load at 210C) was 3.7 g/10 min).
Example 10 The process of Ex 1 was repeated with a set temperature of 200C

203~

and RIGIDEX HD 6007 polyethylene and 30 pph of WINGSTAY L antioxidant and separately for comparison 30 pph of IRGANOX 1076 antioxidant. The levels of non extractable antioxidants wera determined to be both 9 pph and the MFR values of the polymer products were 18.2 g/10 min and 1.78 g/10 min respectively.
Example 11 The process of Ex 1 was repeated with a set temperature of 180C
and 3 pph of 1,3-bis~t butyl peroxyisopropyl)benzene instead of the DCP. The level of non extractable antioxidant was determined to be 10 7.3 pph and the MFR of the extracted polymer product was 18 g/10 min.
Comparative Example R
The process of Ex 6 was repeated with the LOWINOX 22N46 antioxidant (as in Ex N) instead of WINGSTAY L and the melt product without extraction was diluted 221 times as in Ex 7 to give a product, 15 whose OIT at 200C was measured to be 4.3 min.
Example 12 The process of Example 1 was repeated with a set temperature of 160C to give a masterbatch with a level of non extractable antioxidant-~f 9 pph and an MFR of extracted product of 18 g/10 minutes.
The masterbatch was melt mixed at 180C with more RIGIDEX HD5502 polyethylene to dilute it to give a final polymer composition containing lOOO ppm of WINGSTAY L antioxidant. The polym~r composition was tested for Yellowness Index by the method of ASTMD
1925 on an Intern. Colour System MICROMATCH apperatus measuring reflectance and set to W&velength of 400-700 nm simulating daylight without W.
Examples 13 and 14 The process of Ex 12 was repeated with IRGASTAB 17 MOK-A product sold by Ciba Geigy (a mixture of a majority of di butyl tin bis (isoctylthio glycollate with small amounts (in total in the range 2-20% of total product) of monobutyl tin tris (isooctylthioglycollate) and tri butyl tin isooctylthioglycollate) added at the masterbatch dilution step in amount to provide 300 ppm or 200 ppm in total of organotin compounds in the final polymer composition. The Yellowness Z03~S

Indices were measured.
The Yellowness Index re~ults were as given below.

Example SampleYellowness Index _ _ HD 5502 additive free - 0.68 Diluted Masterbatch59 13 Diluted masterbatch with 15 IRGASTAB 17 MOK-A (300 ppm) 1014 As Ex 13 but 200 ppm IRGASTAB 17 Example 15 The process of Example 1 was repeated in a Bambury mixer under nitrogen at 200C set temperature and rotor speed of 200 rpm for 2-3 15 min with a charge of total weight of 2.5 kg of RIGIDEX HD6007 polyethylene, 30 pph Wingstay L antioxidant and 3.75 pph DCP as initiator. The level of non extractable antioxidant was 10.4 pph and the MFR of the extracted polymer product was 7.4 g/10 min.
_ . .

Claims

Case 7386(2) The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-l. An oxidatively stabilized polymer composition comprising an olefin polymer and an antioxidant characterized in that the antioxidant comprises a polymer of dicyclopentadiene and a phenolic compound, at least some of the antioxidant being in a form non extractable with cyclohexane.
2. A composition according to claim 1 characterised in that it is obtainable by reacting in the presence of a radical initiator and in the melt phase said olefin polymer and said antioxidant.
3. A composition according to claim l or 2 characterised in that it is cross linkable and the olefin polymer is a polyethylene with a major proportion of ethylene.
4. A composition according to claim 3 characterised in that the polyethylene is high density polyethylene.
5. A composition according to any one of the preceding claims characterised in that the phenolic compound is phenol or a mono methyl or ethyl phenol.
6. A composition according to any one of the preceding claims characterised in that the antioxidant has terminal phenolic units and has been endcapped with a tertiary butyl hindering group ortho to the phenolic hydroxyl group.
7. A composition according to any one of the preceding claims characterised in that the antioxidant is present in amount of 0.1-100 parts per hundred parts of olefin polymer.
8. A masterbatch composition according to claim 7 characterised in that the antioxidant is present in amount of 3-60 parts per hundred of of olefin polymer.
9. A polymer composition which comprises a blend of a composition according to any one of the preceding claims characterised in that it also contains an olefin polymer.
10. A composition according to any one of the preceding claims characterized in that it comprises at least one organotin compound which is an organotin carboxylate, thioether, oxide or sulphide.
11. A composition according to claim 10 characterized in that the organotin compound comprises a di alkyl tin bis (mercapto alkylene carboxylate ester).
12. A composition according to claim 10 or 11 characterized in that the weight ratio of dicyclopentadiene phenolic polymer to organo tin compound is 1 : 0.1 - 1.
13. A composition according to any one of claims 10 - 12 characterized in that it contains 100 - 1000 ppm in total of the organotin compound based on the total weight of olefin polymer.
14. A method of making an oxidatively stabilized polymer composition comprising an olefin polymer and antioxidant characterised by comprising reacting in the presence of a radical initiator and in the melt phase, said olefin polymer with antioxidant, which is a polymer of dicyclopentadiene and a phenolic compound.