IE42824B1

IE42824B1 - Organic phosphites and their use as stabilisers

Info

Publication number: IE42824B1
Application number: IE1126/76A
Authority: IE
Original assignee: Hoechst Ag
Priority date: 1975-05-30
Filing date: 1976-05-28
Publication date: 1980-10-22
Also published as: NL7605608A; LU75049A1; GB1532709A; BE842413A; DE2523910B2; DE2523910C3; IT1060731B; DE2523910A1; FR2312504A1; BR7603415A; CA1073921A; JPS51143622A; IE42824L; DK235376A; ZA763174B

Abstract

1532709 Stabilizers for polymers; triphosphite esters HOECHST AG 28 May 1976 [30 May 1975] 22414/76 Heading C3K [Also in Division C2] Organic polymers, preferably chlorinated polymers and polyolefines are stabilized by phosphorus compounds of Formula I where A, B and C independently are (i) a radical of Formula II or III or or (ii) an optionally substituted aryl, cycloaliphatic, or aliphatic hydrocarbon group; Rand R1 independently are H or an optionally substituted aryl, cycloaliphatic or aliphatic hydrocarbon group the sum of the C atoms in R and R1 not exceeding 60; X is a straight chain aliphatic hydrocarbon group; at least one of A, B and C is as (i) above and the total C atoms in A, B and C is at least 10; or a mixture of compounds of Formula I above. In the examples, polyvinyl chloride and polypropylene are stabilized.

Description

This invention relates to organic phosphite stabilisers.

Heat and light have a detrimental influence on synthetic polymers. In order to limit this as much as possible, stabilisers and stabilising additives are added to the polymers to prevent degradation. It is known that synergistic effects may be achieved by the combined addition of stabilisers and stabilising additives. The commonly applied stabilising additives are, for example, epoxy compounds, antioxidants, compounds absorbing ultra-violet radiation, and organic phosphites.

However, the stabilising additives are very often . not entirely satisfactory, some having a number of shortcomings. For example, a series Of known organic phosphites which are used for stabilisation purposes show insufficient resistance to hydrolytic influence and a relatively high degree of volatility. Moreover, some of these phosphites are not entirely satisfactory from a physiological point of view.

The present invention provides a phosphite of the general formula B-0-Ρ (I) wherein A, B and C, any two or more of which may be the same Or different, each represents (i) a radical of the general formula R—C-C--R' or Η-C--C_ Η OH OH (ID (III) or represents (ii) an aryl group or a cycloaliphatic or aliphatic hydrocarbon group, e.g. cycloalkyl or alkyl, which may be substituted, wherein R and R', which may be the same or different, each represents a hydrogen atom, an aryl radical, a cyaloaliphatic hydrocarbon, e.g. cycloalkyl, radical or an aliphatic hydrocarbon, especially an alkyl, radical which may be substituted, and wherein the sum of the carbon atoms included in R and R’ does not exceed 60, and wherein X represents a straight-chain aliphatic hydrocarbon, e.g. alkylene, radical, and wherein at least one of A, B and C represents a radical of the formula II or III, and wherein the total number of carbon atoms included in the radicals A, B and C is at least 10, or a mixture of such compounds.

We have found that, to a large extent, phosphites of the general formula I have good stabilising effects and do not have the disadvantages of the known phosphite stabilisers.

The present invention also provides a stabiliser composition containing a phosphite of the present invention and a suitable carrier, a process for stabilising an organic polymer wherein there is used the above phosphite stabiliser or composition and a polymer thus stabilised.

A special advantage of a phosphite of the present invention is its resistance to hydrolytic influence, which is substantially larger than that of many other phosphite stabilisers, a property which improves the weathering properties of moulding compositions which are stabilised with a phosphite of the invention.

A further advantage is that such phosphites of the present invention that are solid at room tenperature impart a better dimension stability under heat to plastic articles using these phosphites than is obtained using known liquid phosphites.

Also, the use Of a phosphite of the present invention reduces substantially tarnishing of the processing machines and the formation of grooves on the shaped articles being produced.

Additional useful properties of a phosphite of the present invention are the general lack of smell, and practical absence of volatility and the lack of tendency to exudation.

The compounds of the present invention are prepared by reacting a compound of the general formula P in which Y, Y' and Y, any two or more of which may be the 20 same or different, each represents an aryl group or a cycloaliphatic or aliphatic hydrocarbon group, with a compound of the general formula or OH OH OH OH in which R, R1 and X have the meanings given above, and, 25 if desired, with a compound of the general formula HO-2, wherein Z represents an optionally substituted aryl, - 5 cycloaliphatic, or aliphatic hydrocarbon group.

Some products of the present invention are still liquid at room temperature; often and preferably, however, the phosphite is a white solid product, some of which have waxlike characteristics. Most interesting are the latter having flow-drop-points of from 35° to 100°C, since in addition to their stabilisation effect, they influence favourably the properties of the products made of polymer moulding compositions containing such wax-like phosphites.

Thus, A may represent a group of the formula II or III and B and C, which may be the same or different, each represents an aryl, cycloaliphatic or aliphatic hydrocarbon radical, or A and B, which may be the same or different, eaoh represents a group of the formula II or III and C represents an aryl, cycloaliphatic or aliphatic hydrocarbon radical, or A, B and C, any two or more of which may be the same or different, each represents a group of the formula II or III. Thus, the compound of the formula I may contain radicals of the formulae II and III, but preferably when at least two of A, B and C each represents the radical II or III, these groups are preferably the same.

An aliphatic hydrocarbon radical, which may be straight- or branched-chain, may be saturated or unsaturated, and may be unsubstituted or substituted, for example by a cycloaliphatic or aryl group. The aliphatic hydrocarbon radical may have, for example, 1 to 60 carbon atoms.

A straight-chain aliphatic hydrocarbon radical represented by X may be saturated or unsaturated and is, for example, an alkylene or alkenylene radical. The aliphatic radical X may have, for example, 3 to 10 carbon atoms.

A cycloaliphatic hydrocarbon radical may be saturated or unsaturated and may be unsubstituted or substituted, for - 6 example, by one or more aliphatic groups, especially alkyl groups. A cycloaliphatic hydrocarbon radical may have, for example, 5 to 12 carbon atoms, especially 5 or 6 carbon atoms.

An aryl radical may be unsubstituted or substituted by one or more of the same or different substituents selected from alkyl, alkoxy and hydroxy groups and halogen atoms, especially by one or more alkyl or alkoxy groups having from 1 to 6 carbon atoms, or by one or more chlorine atoms or by one or 'more hydroxy groups. An aryl radical may have, for example, 6 to 15 carbon atoms, especially 6 to 12 carbon atoms.

For example, if only the radical represented by A has one of these formulae II or III, B and C may be the same or different and each may represent an alkyl group having from 1 to 60, preferably from 1 to 30, carbon atoms, an aryl group having from 6 to 15, preferably 6 to 12, carbon atoms, and a cyeloalkyl group has 5 to 12, preferably 5 or 6, carbon atoms. The aryl group· may be unsubstituted or substituted by one or more of the same or different substituents selected from alkyl and alkoxy radicals having preferably from 1 to 6 carbon atoms.

If A and B have formulae II and/or III, C may be one of the above-mentioned radicals or may also have the formula II or III.

Preferably one or two only of the radicals represented by A, B and C have formula II or III.

In formula II, R and R1 may have the same or different meanings, and each may represent a hydrogen, an aryl group having from 6 to 15 carbon atoms which may be unsubstituted or substituted by one or more of the same or different substituents selected from alkyl and alkoxy groups having 43834 - 7 preferably from 1 to 6 oarbon atoms, chlorine atoms and hydroxyl groups, e.g. a phenyl, tolyl, xylyl, tert.-butylphenyl, nonylphenyl, chlorophenyl or hydroxyphenyl group. Furthermore, R and R' each may represent a saturated or unsaturated, substituted or unsubstituted, cycloaliphatic hydrocarbon radical having from 5 to 12 carbon atoms, e.g. a cyelopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or cyclododecyl radical, or a straight-chain or branched-chain alkyl radical having from 1 to 60, preferably from 8 to 40, and especially from 8 to 20, carbon atoms, such as, for example, the ethyl, butyl hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl, triacontyl, dotriacontyl, tetratriacontyl, hexatriacontyl, octatriaoontyl, tetracontyl or dotetracontyl radical. The sum of the carbon atoms contained in R and R' should not exceed a maximum of 60, preferably of 40.

If R' represents a hydrogen atom or a methyl or ethyl group, R preferably represents an alkyl, preferably a straight-chain alkyl, group having from 6 to 58, preferably from 18 to 40, and especially from 20 to 36, carbon atoms. Structures of this kind, wherein R1 represents a hydrogen atom, are suitable for incorporation into the phosphite through the corresponding 1,2 diols, which may be prepared, for example, from the corresponding epoxides by adding water.

If use is made of epoxide mixtures such as are obtained for example by epoxidising mixtures of commercially available long-chain α-olefins, mixed products are obtained the structure of which may be designated, for example, as C2O/24“a:1'ky'1·-,,' C18/22H37/45-' C30+ cf. Table for Examples 2-14, footnotes 3, 4 and 5 428Ξ-1 - 8 In the radical A and optionally also in B, and also optionally in C, preferably when R' represents a hydrogen atom or a methyl or ethyl group and R represents an alkyl group having from G to 58 carbon atoms, the remaining t and optionally B .groups are alkyl groups having from 1 to carbon atoms.

\ In formula III X represents a straight-chain saturated (alkylehe) or unsaturated aliphatic hydrocarbon radical having from 3 to 10, preferably from 5 to 7 carbon atoms. A group of structure II is, for example, the j a-hydroxy-cyclohexyl radical.

A further characteristic of a phosphite of the present invention is that the total number of carbon atoms contained in the radicals A, B and C amounts to at least , preferably to at least 16.

The following phosphites are examples of compounds of the general formula I: ft ι 42834 s -O TABLE A CM ch to CM CJ a T to tQ «rt 0—0 O Φ p •rt Λ & to o XJ ft >1 O X! & xj rrt >1 Φ Ή flj X Φ XJ & CM a a i a a ο—o ι σ» CM a irt u Φ P •rt xi & CQ q jl >1 1Λ l£> CM to o ws CM o in y ft a o CM CM ft ϋ CM 0 o T *w«* o CM ft 1 a o CM o 1 a 1 CM o a a T o— 0 a to cn T o- -o cn a a cn ffi 0-0 cn cn «Ρ rrt Φ P •rt XS ft CQ XJ ft •q φ P cn ®A <0 H φ P •rt XJ ft ω o •g ft >< □ φ Ό nJ P ϋ ? +1 •rt xS ft 0? jl Ό Φ P ft m CM a Ϋ ξ-g cn cn CM a V g-§ I in t*. cn a CM § rrt o Φ P •rt in <0 o o ft CM O CM a o a a 0—0 I in t* cn a CM CM \ rrt u 0) +1 •rt XJ 8· CJ ft xi CQ ft 0 Φ fi rrt P to fr •rt AJ XS irt rrt ft fr flj &Γ X 1 0 rrt xs flj CM ft 1 Xf o (rt CM CM >1 O I 8 CM fr Ό O X nJ I 0 P fr 3 nJ •v o V P Φ P *g 0 X Ό Ό x: 0 V >1 0 0 >t >i n >1 XJ & li 5? XJ & Ό XJ 1 X Ό o 0 >. 1 CM 0 & p CM li Xi CMx-x 5 •9 Ό I CQ Ό 1 CQ >1 CM CQ •rt fr CM £ •rt XJ V—- •rt *9 XJ I rQ 1 irt P 1 1 rd CM CM >1 1 rrt CM fr rrt χ* «rt xi, CQ >1 CQ P >1 ti CQ P •rt XJ •rt Φ xi Φ •rt Φ P p p •rt P XS P •rt P Φ P Ό Φ ft P *0 £ I CM CQ •rt -? trt & Ο) x: ft - 10 (Continued) cn O I d ffi U ffi ffi 0-0 . in Γ* co ffi ci <0 H Ό o £ ft.

V CM « O a a o—o cn in > a* VD CI \ CI d ffi □ I ffi ffi 0—0 I cn in \ in xh vp d \ CJ Cl o in d ϋ d ffi o d m ft in o ffi d ffi o VD «—» d ft ϋ o □ d o 1 o o ft ffi d ft CM O ϋ ffi o a CM I O d o a ώ a T ffi 1 o Ο- -o ffi ffi o a a I ι Ο- O 1 0—0 a a H ι ffi a 0—0 vD cn U- -o 10 1 tt m > a* CM o cn ι-ί VD O tn O cn Φ ffi •ri ffi 8* a υ Φ d ( Φ ffi d -P φ •H ϋ (V . *rl ffi ffi P ffi •H ft •H & λ UJ Φ ffi 5y ft 0 fi ft 0 ω ffi •H ω ffi 0 ft ffi 0 ft ffi ft ffi *—S ft rd tn ^ft H I 0 S rd ffi ffi H ffi >1 fi ft >1 fi ffi rt ffi rt r-l l fi I rt 00 >1 rt l d ffi 1 + co H O ) Φ ffi •H ffi ft ω o ffi ft r-i £ l-i rt ι φ ffi •Η ffi ft ω Ο ffi ft Η rt I ο d ffi ϋ ffl ffi 0-0 φ κο cn υ ί Xj* d 1 Cl xj· O 00 \ d 1 ci o o N \ d 1 X xi* J 0 d O cn O cn ο tn υ I -alkyl) pho sphite ο cn i 5? p O &· P 0 •a a o •3 1 0 «σ P I 5? p >1 P >1 Ό ffi o •σ ffi 5? Ό 4 >1 1 & p 1 0 N l d p *0 ffi d P ffi d f —*· P l Tf 1 *—* - d 02 Ό ffi d ra >» d (Q *-<* •ri rj, 1 •H ffi *—* •ri r-l *9 *? Cl fi ffi I r-i ffi >1 1 1 >«» Ί d >1 1 β η d Y ffi r-I ffi H Φ >1 ra ffi >1 m ffi >1 ffi β ra •H Φ ffi •ri Φ ffi ft Φ •ri p •ri ffi P ‘H ffi •H ffi P ffi T3 Φ ffi Ό Φ Π3 ft ffi ιη -lift phosphite of the present invention may be used alone or in admixture with one or more phosphites of the invention and/or with one or more other additives selected from known stabilisers, stabilising auxiliaries, antioxidants and ultra-violet-stabilising conpounds, and/or with a lubricant, plasticiser, pigment or filler or mixture of two or more such additives.

Preferably there are used from 0.01 to 10 parts by weight of compound of formula I per 100 parts by weight of organic polymer.

When chlorinated polymers, such, for example, as chloropolyethylene, rigid and soft polyvinyl chloride, polyvinylidene chloride, polyvinylchloroacetate and vinyl chloride-a-olefin-copolymers are processed, a substantially improved stability to heat and to light is achieved by adding a phosphite of formula I, in the presence of a compound known as stabiliser, such, for example, as a metal compound, an indole substituted in the 2-position, preferably 2-phenylindole, an epoxide stabiliser, a polyhydric alcohol, or a mixture of two or more such compounds.

Suitable metal compounds known as stabilisers are, for example, Ca, Ba, Sr, Zn, Cd, Mg, Al and Pb soaps of aliphatic carboxylic acids or oxycarboxylic acids having from 8 to 32 carbon atoms, preferably from 8 to 24 carbon atoms, salts of these metals with aromatic carboxylic acids of preferably from 7 to 12 carbon atoms, e.g. benzoates, salicylates as well as (alkylJphenolates of these metals, the alkyl radical having from 1 to 12, preferably from 1 to 6, carbon atoms. This range of compounds also includes organo-tin compounds, e.g. dialkyl-tin-thioglycolates and carboxylates as well as -optionally-neutral and basic lead salts of inorganic acids such, for example, as sulphuric acid and phosphorous acid. - 12 Known epoxide stabilisers are, for example, higher epoxidised fatty acids such, for example, as epoxidised soybean oil, tall oil or linseed oil,epoxidised butyloleate and higher epoxyalkanes.

Polyhydric alcohols are, for example, pentaerythritol, trimethylol propane, sorbitol or mannitol, i.e. preferably alcohols having from 5 to 6 carbon atoms and from 3 to 6 OH groups.

Stabilisers of this kind, e.g. metal compounds, epox10 ides and polyhydric alcohols are described, for example, in J. Voight Stabilisierung der Kunststoffe gegen Licht und Warme, Springer-Verlag, Berlin-Heidelberg-New York (1966).

A very efficient stabiliser composition for processing halogenated polymer moulding compositions consists, for example. Of from 0.01 to 10 parts by weight of a phosphite of formula I, 0.1 to 10 parts by weight of a metal compound known as stabiliser, 0.1 to 10 parts by weight of a known epoxide stabiliser and 0 to 1 part by weight of a polyhydric alcohol.

A phosphite of the present invention displays also an excellent efficiency for stabilising polymers or copolymers of olefins free from halogen. The stability of, for example, polypropylene to heat and to light is considerably improved by the addition of a phosphite of formula I, especially in admixture to phenolic and/or sulphidic stabilisers.

Suitable phenolic and sulphidic stabilisers are, for example, the generally known stabilisers against heat and light which are used in the processing of plastics, for example 3,5-ditertiarybutyl-4-hydroxyphenyl-propionic acidester, 2,6-ditertiarybutyl-p-cresol, alkylidene-bis-alkyl42824 - 13 phenols, esters of bis-(4'-hydroxy-3'-tertiary-butylphenyl)butyric acid, thiodipropionic acid ester of fat alcohols as well as dioctadecyl sulphide or dioctadecyl disulphide; ef. J. Voigt, Stabilisierung der Kunststoffe gegen Licht und Warme, Springer-Verlag, Berlin-Heidelberg-New York (1966).

A synergistically efficient stabiliser composition for polymers or copolymers of olefins free from halogen consists, for example, of from 0.05 to 5 parts by weight of a phosphite according to the invention, from 0.05 to 3 parts by weight of a known phenolic stabiliser and/or of from 0.1 to 3 parts by weight of a known sulphidic stabiliser. Special stabilisers against ultra-violet rays may also be added to the stabiliser composition In an amount of from 0.1 to 3 parts by weight, if deemed necessary. Known ultra-violet absorbers are, for example, alkoxy-hydroxybenzophenones, hydroxyphenylbenzotriazoles, salicilic acid phenolic ester, benzoic acid hydroxyphenolic ester, benzylidene malonic acid mononitrile ester as well as so-called quenchers11 such, for example, as nickel chelates, hexamethyl-phosphoric acid triamide or - as recently made known - piperidine stabilisers.

Stabiliser compositions of the phosphites according to the invention and known stabilisers not only improve the stability of polyolefins, chloropolyolefins and chlorinated vinylpolymers, but impart also an improved stability Of polyesters, polyamides, polyacrylonitrile, polycarbonates, polysiloxanes, polyethers, and polyurethanes.

The following Examples illustrate the invention; EXAMPLE 1; A 1 litre four-necked flask, equipped with an agitating device, an internal thermometer, gas inlet and descending - 14 cooler, was purged with nitrogen and subsequently charged with 429 g (1.5 mole) of octadecane-1,2-diol and 83 g (0.5 mole) of freshly distilled triethyl phosphite. The contents of the flask were heated to 115-12O°C in the course of 20-30 minutes in a weak nitrogen current, while stirring, ethanol then starting to separate at an internal temperature of about 110°C. Within a further 3-5 hours, while stirring was continued, the temperature of the reaction mixture was slowly increased from 120°C to a final temperature of 160°C. 66.2 g of ethanol were distilled off during this period of time. Agitation was then continued for another hour in a water jet vacuum of 10-20 mm at the unaltered temperature of 160°C, in order to remove possible volatile components. After this period, 3.1 g of a clear liquid consisting of 1.2 g of triethyl phosphite and a further 1.9 g of ethanol were found in.a cooling trap set up between the described apparatus and the water jet pump.

Thus a total quantity of 68.1 g (98.6% of the theoretical yield) of ethanol was separated.

After cooling down the limpid, slightly yellowish melt 438 g (98.8% of the theoretical yield) of tris-(2-hydroxyoctadecyl Jphosphite were obtained as a white wax having a flow-drop-point of 59.5-61°C (determined according to DGF M III 3(57)), containing 3.3% of phosphorus, and having a molecular weight of 854. The calculated values for a compound of formula Ο,,.Η. Π1Ο.Ρ, are 3.5% P and a molecular □4 XXX b weight of 886.

EXAMPLES 2-14: Further phosphite compounds were prepared according to the method described by Example 1. The following Table shows the preparation details and the analysis of the products obtained by the processes. in κθ mF m in Ρ» t— «. co o co m mF 1 1 rd 1 KO m mF mF m m P* in 1 I 1 I K 1 ω t- mF co in co rd mF in m mF mF P- P* P' ω Ό β 00 Ρ» co CM Q in «# o β CO co ro O CM LO Ol Ο ΚΟ Γ— Κ0 V rd 00 in oi Ή rd MF CM KO KO O o ω co CO O O CM Γ- ι-d CO KO 00 KO mF CM ΟΟ in O rd rd mF KD CO K0 mF O P^ CM CM rd I» ro CM s in oo CM mF K0 r— in CM KO cn O io O co - Ό Φ Φ Χί β 43 -H β Ή 43 °s ο ω •η φ 43 4J β ·Η #& Μ ο Φ XJ Α 04 ο & £ I CM « Ο $ i? Ό >1 1 fb —. >1 rd *—* rd ω td Ί CM r-i J3 >1 •H □ —' >1 1 rd 1 0 Λ Φ rd ϋ CM >1 CM Φ 1 Ό td Φ O Ό rd β J2 Ό (fl Φ (fl β M μ Φ β -r| « χί ϋ Φ 43 & 0 *0 £ Φ XJ s? •H 0 A O Ο rd ££ X rd Ο *Ο I &Η —* Η α β •Η I ο Μ Ό I Λ £ Η I β 1 1 co rd 1 CM co *? CM 00 CM rd \ XJ cm (fl \ id mF fi \ •rl mF X! CM Φ M· έ! CM U SV •id A CM o £ SV Ο Μ Ό Ν Ύ .

CM **> *-* Η •3^ ? Φ Φ •μ >ι •ri μ Λ -ri &S.3 Ο β s&'gg Φ Φ •σ ό μ Φ φ Φ Ο> >ι >ι —ί ΟΟΟ Uft* g g.s co co \ m co co in mF CM < m r> KO § O' co mF p* \ m mF KO KO § co m Φ xi >1 •rl β β IQ 3 Ό ΉΗ &C Cfl Q Φ φ θ' § 1 Ο CM ϊ>Ί Η Ο Q •Ρ β β rd ft ι & β α Φ -rd co ο co X in rd \ CM rd u a fri co •χ in * rd \ κθ rd u σι CM m rd d o rd o ft ft & cu cu 0 w H w Ed Ed E< Ed EH O o O KO KO o CO co mF CM \ X. \ 00 Oi Oi o mF * X KO o o o co X σΓ < o * rd >0 oH co 00 00 CM CM CM 'v· X X X +Λ mF mF df o CM CM CM co υ υ u o KO r— 00 oi • ο £ο Ό • · Η fc fc in 10 00 tn 00 r> iP 1 iP I 00 in in Φ in I 1 l o xr σι 10 00 in m ω 00 cn Η ιη φ ιη Ο co χΤ ιη φ σι xr xr co 00 10 σι r- σι co xT Φ r* 10 o ip Ip σι cn r* CM xT * H xr cn xr CM ip in o Tf Φ CM xr xT xr CM ω § ft ι υ CM I ’Φ CM X! Ρ •Η & Ui r4 Ο Ή Ρ ι CM W £ Ο Ρ Λ I ϋ Μ* CM Ο CM XJ Ρ •Ρ W Η Ο •Ρ Ω ο Φ ρ κ Η S ό φ φ Χ2 β 4J ·Ρ ra «Ρ Ο Α Ο β Ο W •Η Φ Πί ϋ .11 01 ο β) χ; Ω ft Ό ·£?>ι ·?£ CM Η 8+ο έίο >!ι . φ CM Ό *-* ra ω ρ •Ρ ϋ >ι ο β Ρ Φ Ό £ δ1 fc χ: I χί* CM CM ϋ fr5? Ο Ρ *α ί CM rp Ο Η ά) ft & £ >ιΗ ft 43 ιβ rd ι—ί &? X +ο ft cn •Η Ο Q I Η ι ra CM + Ο (0 cn Η ϋ •9 ί Λ & ί? 8 Φ Ό £ £ ft ϋ tp ο φ Ρ S Φ +> >ι Η +ι Λ ·Η &ft.S Ο Λ _ Ιβ Ό Ό φ φ φ >, >irW οοο 7* *3 S Φ Φ -rl Φ -μ •Η Λ & σ Λ & φ X! .8* Ρ £4 ή g ft I ϋ ο cn s ? ft CO in «, iP in O in Φ m rP m in \ cn \ < cn O in o in d CM o H O fc fc fc fc ft fc fc fc fc ft & E4 £i A fc fc &4 >1 •μ •Η Φ -Ρ β Χί β *Η ρ ra w a Ό w η σ’ β g οο ra ra •κ «ο Ρ W Q φ Φ tn g 1 >«Η Ο cm Ο Q •Ρ Ή g ra η ft Ο § -Ρ ό σι xr cn CM CM cn \ co 00 xr o xT \ \ G\ 10 rp o o * co \ < Ο σι Ο Η \ Η ϋ χί· CM CM Ο +ο cn ϋ Μ Ο fc Ζ Η r4 CM Η φ Ρ •Ρ X! & Ο Λ a ι-ί £ φ Η £ £ +· m ο ft Β m |p O •P ? CM fc fc £4 Φ P I •rl a +1 a •P ft §· ft > § rp cn Η 42834 - 17 EXAMPLE 15: The stability to hydrolysis of a number of phosphites of the present invention, and, for comparison, the stability of four commercially available products, was determined as follows: g of phosphite were heated to boiling point in 100 ml of distilled water; after having boiled for 20 to 60 minutes, the reaction mixture was cooled and the phosphorous acid content of the aqueous solution determined by titration with aqueous 0.1 N-sodium hydroxide solution. The degree of hydrolysis of the phosphite submitted to the test is determined as 100 x/y, x being the actual volume of 0.1 N-NaOH consumed and y being the volume of this reagent calculated for complete hydrolysis of the phosphite to yield phosphorous acid.

Phosphite Degree of hydrolysis in % after a boiling time of 20 Min. 60 Min. (a) X ( ) Triphenylphosphite 84 100 (b) (1) Tris(nonylphenyl)phosphite 57 92 (c) (^) Diphenyl-isooctylphosphite 55 77 (<3) (1) Distearyl-pentaerythrityldiphosphite 52 68 (e) Ethyl-bi s(2-hydroxyoxyoctadecyl)phosphite 33 42 (f) Diethyl-(2-hydroxyoctadecyl)phosphite 21 30 (g) Tris(2-hydroxy-C24y28-alkyl)phosphite ' 35 51 (h) Ethyl-bi s(2-hydroxy-C . alkyl)phosph. ' 31 ' 41 (i) Diethyl-(2-hydroxy-C . ,alkyl)phosph. ' 25 36 (j) Ethyl-bis(2-hydroxy-C_ + -alkyl)pho sph. 11 13 Ot) Tri s—(2-hydroxy-C3Q+-alkyl) phosphite 16 23 (1) Phenyl-bis(2-hydroxy-C3Q+ -alkyl)phosph. 12 13 (1) Commercially available products as comparative substances. - 19 EXAMPLES 16 to 39: These Examples illustrate the stabilising effect of phosphites of the present invention on the processing of polyvinyl chloride. The dynamic stability under heat (Examples 16 to 27) and the static stability under heat (Examples 28 to 39) were determined. The specified parts are parts by weight.

For each of a number of phosphites of the present invention, 100 parts of a mass-polyvinyl chloride having a K-value of 60 were mixed thoroughly with 0.2 parts of 2-phenylindole, 3 parts of epoxidised soybean oil, 0.25 parts of a complex calcium/zinc stabiliser consisting of 42 weight % of calcium stearate, 30 weight % of zinc stearate, 22 weight % of pentaerythritol and 6 weight % of 2,6-di-t-butyl4-methyl-phenol, 0.2 part of a montanic acid ester (acid number 18, saponification number 154), 0.3 part of stearyl stearate, 0.5 part of glycerolmonostearate, and 0.5 part of the phosphite.

In order to determine the dynamic stability under heat each mixture was applied on to a laboratory-scale twinroller device heated to 180°C, and rolled-out to a sheet within one minute at 20 rmp. At intervals of 10 minutes, spot samples were picked of these sheets, and their colour shades compared with an internal colour chart. The various tests were run until the rolled-out sheet had taken up a dark-brown to black shade.

In order to determine the static stability under heat, a rolled-out sheet was first prepared from each mixture according to the description given above, and this sheet was rolled out on the twin-roller device at 180°C for another 10 minutes' period. The sheet was then peeled off the roller and sheets of about 0.5 mm thickness and a diameter - 20 of 30 mm blanked therefrom. The sheets were wrapped in an aluminium sheet and tempered at 180°C in a heating cabinet with internal air circulation. One sheet was selected every 10 minutes and its colour shade compared with the colour chart. The figures employed in the colour chart have the following meaning: = water-white = slightly yellowish = distinctly yellow tint 4 = dark yellow-bronw shade = dark brown to black As demonstrated by the following Tables, as far as dynamic stability and stability under heat are concerned, the polyvinyl chloride stabilised by organic phosphites of the present invention is clearly superior in comparison to polyvinyl chloride stabilised with known phosphites and with mixtures free from phosphites. - 21 42824 +J ti •P φ φ xi fi y-i ?0 Π3 Φ Φ 6 r-i ·η r-i -P O P Φ Λ P fi o •r| •P ti P fi 0 r-i O 0 0) •P P tn in in in ι 1 ϊ I tn l ntf xt mcncnromcococntn cn co cn cn cn rn cn rn ι ι ι t co ι CM CM CM CM CM cn co cn tn m I I I CM CM CM I I CM CM CM CM CM CM CM CM CM CM CM CM CM I I I CM CM I r-i r-i Η H ΗΗΗΗΗΗΗΗΗ in m in CM CM H r-i CM Dynamic stability under heat lD>C0G)OH HHHHCMCMCMCMCM ti U in in H rd •P fi *§ •P •ri £ M-4 428 2 4 - 22 Static stability under heat Discolouration of the sheet in the heating cabinet with air-circulation at a tempering period of ,οοτ as compared to colour chart figure 1 I 1 ι ι ι tn t m m m ι ι ι ι ι 1 1 . o co 1 tf l tn in m in in ω cn ι tn ι 1 i i cn 1 1 1 1 70' 1 1 mcncncncncncncnmi im i 1 1 δ \0 1 cn cn cn cn cn cn cn cn I tf ι ι ι tmi ι ι ι ι in ι in CM CM CM CM CM CM CM CM 1 CQ I .OS m cn cn m cn cn cn cn m · tf ι ι ι ι ι ι i ι ι ι cn cn ι CMCMCMCMCMCMCMCMCMl CO i 40' J 1 mcnmmcncncncncnicn cn ι ι ι ι ι ι ι i i ι ι cm < CMCMCMCMCMCMCMCMCMICM cm 30 1 ι cn CMCMCMCMCMCMCMCMCMl CM CM 1 1 CM 1 1 1 20' 1 CM CM 1 CM CM CM CM 1 CM I CM CM CM 1 1 CM CM 1 rd rd 1 rd I ! 1 O 1 1 1 rdrdrdrdrdrdHrdrd j rd rd rd ) Phosphite according to : Example 1 1 I 1 I 1 P 1 —· ~ β ι rt ο o CMCnrdrdinv0r* Example No . 1 1 P Md P 10 0 0 COCPOrdCMCntfiniOl CMCMcncncn cncncncni 1 γ*· co σ» l cn cn cn ί - 23 EXAMPLE 40: This example shows that the addition of a phosphite of the present invention to polypropylene improves considerably its stability to light and against alterations due to heat.

A powdery mixture consisting of 100 parts by weight of unstabilised polypropylene [i5(2300C)aboUt 8] 0.15 part by weight of octadecyl-3-(3',5'-di-tert.-butyl-4'hydroxyphenyl)-propionate and 0.10 part by weight of the ethyl-bis(2-hydroxy-C24/2g-alkyl) phosphite prepared according to Example 7 was injection-moulded on an injection moulding machine to yield test plates measuring 60 x 60 χ 1 mm. Test specimens were blanked from these plates.

The stability to light was determined by means of the Xeno-test device, type 150, produced by Messrs. Hanau Quarzlampen GmbH with the filter combination 6 IR + 1 UV as per Din 53 387. (DIN = German Industrial Standard).

The time of exposure to light, i.e. the period of time after which the absolute elongation at break had decreased to 10% was measured in hours. In the case of polypropylene stabilised with ethyl-bis(2-hydroxy-C24/28~alkyl)phosphite this time of exposure amounted to 695 hours. Comparative specimens which had been prepared according to the abovespecified recipe - but without ethyl-bis(2-hydroxy-C24/2galkyl)phosphite - reached only 540 hours for this time of exposure.

The resistance to alteration under heat of injection moulding test samples was measured approximately to the procedure described by DIN 53 383 at an air temperature of 140°C. In the ease of polypropylene stabilised with ethyl~bis(2-hydroxy-C24/2g-alkyl)phosphite, the resistance 42834 - 24 amounted to 40 days to total embrittlement; the resistance to alteration under heat of comparative sanples was 22 days

Claims

1. CLAIMS:1. A phosphite of the general formula ABC- (I) wherein A, B and c, any two or more of which may be the same or different, each represents (i) a radical of the general formula Η Η X II / \ R C_C—R' or H—-C--C — H I I I OH OH (II) (HI) or represents (ii) an aryl group or a cycloaliphatic or aliphatic hydrocarbon group which may be substituted, in which R and R', which may be the same or different, each represents a hydrogen atom, an aryl group, or a cycloaliphatic or aliphatic hydrocarbon group which may be substituted, and wherein the sum of the carbon atoms in R and R' does not exceed 60, and X represents a straight-chain aliphatic hydrocarbon radical and wherein at least one of A, B and C represents a radical of the formula II or III, and wherein the total number of carbon atoms included in the radicals represented by A, B and C is at least 10, or a mixture of such compounds.

2. A compound as claimed in claim 1, wherein an aliphatic hydrocarbon group is saturated or unsaturated and may be substituted by a cycloaliphatic or aryl group and which may have 1 to 60 carbon atoms, and which may be straight- or branched-chain. - 26 43834

3. A compound as claimed in claim 1, wherein a cycloaliphatic hydrocarbon group may be saturated or unsaturated, and may be substituted by one or more aliphatic groups, and which may have 5 to 12 carbon atoms.

4. 5 4. A compound as claimed in claim 1, wherein an aryl group may be substituted by one or more of the following substituents: alkyl, alkoxy, hydroxy, and halogen, and may have 6 to 15 carbon atoms. 5. A compound as claimed in claim 1, wherein at least 10 one of A, B and C has the general formula II, and in the or each group of formula II, R and R', which may be the same ot different, each represents a hydrogen atom, an aryl group having from 6 to 15 carbon atoms, an unsaturated or saturated cycloaliphatic hydrocarbon group having from 5 to 12 15 carbon atoms or an alkyl group having from 1 to 60 carbon atoms.

5. 6. A compound as claimed in claim 5, wherein an aryl group representing R and/or R' is unsubstituted or substituted by one or more substituents, any two or more of which 20 may be the same or different, selected from alkyl, alkoxy and hydroxy groups and chlorine atoms.

6. 7. A compound as claimed in claim 6, wherein the aryl group is unsubstituted or substituted by one or more alkyl or alkoxy groups having from 1 to 6 carbon atoms. 25

7. 8. A compound as claimed in any one of claims 5 to 7, wherein a cycloaliphatic hydrocarbon group representing R and/or R 1 is a cycloalkyl group having 5 or 6 carbon atoms.

8. 9. A compound as claimed in any one of claims 5 to 8, wherein an alkyl group representing R and/or R' has from 30 8 to 40 carbon atoms,

9. 10. A compound as claimed in claim 9, wherein the alkyl group has from 8 to 20 carbon atoms. - 27

10. 11. A compound as claimed in any one of claims 1 to 10, wherein at least one of A, B and C has the general formula II and in the or each group of formula II R and R' together have no more than 40 carbon atoms.

11. 12. A compound as claimed in claim 5, wherein in the or each group of formula II, R* represents a hydrogen atom or a methyl or ethyl group and R represents a straightchain alkyl group having from 6 to 58 carbon atoms.

12. 13. A compound as claimed in claim 12, wherein R represents a straight-chain alkyl group having from 18 to 40 carbon atoms.

13. 14. A compound as claimed in claim 13, wherein R represents a straight-chain alkyl group having from 20 to 36 carbon atoms.

14. 15. A compound as claimed in any one of claims 1 to 14, wherein at least one of A, B and C has the general formula III and in the or each group of formula III X represents a straight-chain unsaturated or saturated aliphatic hydrocarbon group having from 3 to 10 carbon atoms.

15. 16. A compound as claimed in claim 15, wherein the aliphatic hydrocarbon group represented by X has from 5 to 7 carbon atoms.

16. 17. A compound as claimed in any one of claims 1 to 16, wherein at least one of B and C does not have the formula II or III and this or each of these groups is an aryl group having from 6 to 12 carbon atoms, a eycloalkyl group having from 5 to 12 carbon atoms or an alkyl group having from 1 to 60 carbon atoms.

17. 18. A compound as claimed in claim 17, wherein an aryl group representing B and/or C is unsubstituted or substituted by one or more of the same or different substituents selected from alkyl and alkoxy groups. - 28 4 282 4

18. 19. A compound as claimed in claim 18, wherein the aryl group is unsubstituted or substituted by one or more alkyl or alkoxy groups having from 1 to 6 carbon atoms.

19. 20. A compound as claimed in any one of claims 17 to 5 19, wherein a cyeloalkyl group representing B and/or C has 5 or 6 carbon atopis. .

20. 21. A compound as claimed in any one of claims 17 to 20, wherein an alkyl group representing B and/or C has from 1 to 30 carbon atoms. 10

21. 22. A compound as claimed in claim 1, wherein A represents a straight- or branched-chain hydroxyalkyl group Of the general formula II wherein R represents an alkyl group having from 6 to 58 carbon atoms and R' represents a hydrogen atom or a methyl group or an ethyl group, and 15 wherein the sum of the carbon atoms in R and R' amounts to from 6 to 60, and wherein B and C, which may be the same or different, each represents an alkyl group having from 1 to 60 carbon atoms.

22. 23. A compound as claimed in claim 1, wherein A and 20 B, which may be the same or different, each represents a straight- or branched-chain hydroxyalkyl group of the general formula II wherein R represents an alkyl group having from 6 to 58 carbon atoms and R' represents a hydrogen atom or a methyl group or ah ethyl group, and wherein the 25 sum of the carbon atoms in R and R 1 amounts each to from 6 to 60, and wherein C represents an alkyl group having from 1 to 60 carbon atoms.

23. 24, A compound as claimed in claim 1, wherein A, B and C, any two or more of which may be the same or different, 30 each represents a straight- or branched-chain hydroxyalkyl group of the general formula II wherein R represents an alkyl group having from 6 to 58 carbon atoms and R‘ represents a hydrogen atom or a methyl group or an ethyl group, and wherein the sum of the carbon atoms 'in R and R r amounts each to from 6 to 60.

24. 25. A compound as claimed in claim 22 or claim 23, wherein the alkyl group represented by C or each alkyl group represented by B and C has from 1 to 30 carbon atoms.

25. 26. A compound as claimed in any one of claims 22 to 25, wherein the alkyl group represented by R has from 18 to 40 carbon atoms.

26. 27. A compound as claimed in claim 26, wherein the alkyl group has from 20 to 36 carbon atoms.

27. 28. A compound as claimed in any one of claims 1 to 27, wherein the groups represented by A, B and C together have at least 16 carbon atoms.

28. 29. A compound as claimed in any one of claims 1 to 28, wherein at least two Of the groups represented by A, B and C are the same.

29. 30. A phosphite of the general formula B'_0-P (I) C'-0 wherein A', B' and C’, any two or more of which may be the same or different, each represents (i) a radical of the general formula H .X' C — R' ,3 or OH OH or represents (ii) an aryl, cycloalkyl, or alkyl group, in 2 3 which R and R , which may be the same or different, each represents a hydrogen atom, an aryl, cycloalkyl or alkyl - 30 group, and wherein the sum of the carbon atoms included in 2 3 R and R does not exceed 60, and wherein X' represents a straight-chain saturated or unsaturated alkylene radical, and wherein at least one of A 1 , B', and C' represents a 5 radical of the formula II or III and wherein the total number of carbon atoms included in the radicals A', B' and C' is at least 10. '

30. 31. A mixture of two or more compounds as claimed in any one of claims 1 to 30. 10

31. 32. A compound as claimed in claim 1 or a mixture as claimed in claim 31, listed in Table A herein.

32. 33. A process fof the preparation of a compound claimed in claim 1, which comprises reacting a compound of the general formula Y-°'\ 15 Y' 0—— P Y-0in which Y, Y' and Y' f , any two or more of which may be the same or different, each represents an aryl group or a cyclo aliphatic or aliphatic hydrocarbon group, with a compound of the general formula H . Η X I I , /\ R—C-C—R or H — C-C —H 20 OH OH OH OH in which R, R 1 and X have the meanings given in claim 1, and, if desired, with a compound of the general formula HO-Z, wherein Z represents an optionally substituted aryl, cycloaliphatic or aliphatic hydrocarbon group. 25

33. 34. A process as claimed in claim 33, wherein Y, Y' and Y“ each represents a phenyl or an alkyl group of 1 to 8, 42834 - 31 preferably 1 to 6, carbon atoms.

34. 35. A process as claimed in claim 33, carried out substantially as described in any one of the Examples 1-14 herein.

35. 36. A compound as claimed in claim 1, whenever prepared by a process as claimed in any one of claims 33 to 35.

36. 37. A stabiliser composition which comprises a phosphite as claimed in any one of claims 1 to 32 and 36, and a suitable carrier.

37. 38. A composition which comprises a compound or mixture as claimed in any one of claims 1 to 32 and 36, and one or more other additives selected from known stabilisers, stabilising auxiliaries, antioxidants, ultra-violet stabilisers, lubricants, plasticisers, pigments and fillers.

38. 39. A composition as claimed in claim 38, wherein the known stabiliser component comprises a metal compound, an indole substituted in the 2-position, an epoxide stabiliser, a polyhydric alcohol or a mixture of two or more such compounds.

39. 40. A composition as claimed in claim 39, for halogenated polymer-moulding compositions, which consists of from 0.01 to 10 parts by weight of the phosphite claimed in claim 1, from 0.1 to 10 parts by weight of a known metallic stabiliser, from 0.1 to 10 parts by weight of a known epoxide stabiliser and from 0 to 1 part by weight of a polyhydric alcohol.

40. 41. A composition as claimed in claim 38, wherein the known stabiliser component comprises a phenolic or sulphidic stabiliser or mixture of two or more such compounds.

41. 42. A composition as claimed in claim 41, for polymers or copolymers of olefins free from halogen, which consists of from 0.05 to 5 parts by weight of a phosphite claimed in claim 1, from 0.05 to 3 parts by weight of a known phenolic stabiliser and/or from 0.1 to 3 parts by weight of a known sulphidic stabiliser.

42. 43. A composition as claimed in claim 42, which contains 0.1 to 3 parts by weight of a known stabiliser against ultra-violet radiation.

43. 44. A composition as claimed in claim 37, substantially as described herein.

44. 45. A process for stabilising an organic polymer, wherein there is used a compound or mixture as claimed in any one of claims 1 to 32 and 36 or a composition as claimed in any one of claims 37 to 44.

45. 46. A process as claimed in claim 45, wherein the polymer is a polyolefin, chloropolyolefin, chlorinated vinylpolymer, polyester, polyamide, polyacrylonitrile, polycarbonate, polysiloxane, polyether or polyurethane.

46. 47. A process as claimed in claim 46, wherein the polymer is a chlorinated polymer and the composition is as claimed in claim 39 or claim 40.

47. 48. A process as claimed in claim 46, wherein the polymer is an olefin homo- or copolymer free from halogen atoms and the composition is as claimed in any one of claims 41 to 43.

48. 49. A process as claimed in any one of claims 45 to 48, wherein there is used from 0.01 to 10 parts by weight of the compound claimed in claim 1 per 100 parts by weight of polymer.

49. 50. A process for stabilising an organic polymer, wherein there is used a compound as claimed in claim 1 in an amount of from 0,01 to 10 parts by weight per 100 parts 42 82 4 - 33 by weight of polymer, optionally combined with one or more additives selected from known stabilisers, stabilising auxiliaries, antioxidants, ultra-violet stabilisers, lubricants, plasticisers, pigments, and fillers. 5

50. 51. An organic polymer which has been stabilised by a process as claimed in any one of claims 45 to 50.

51.

52. A plastic moulding composition which contains as stabiliser a phosphite as claimed in claim 1.